JP2008272948A - Thermal transfer ink sheet and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal transfer ink sheet which can eliminate blocking without causing ribbon creases and can attain a print of a high image quality, and an image forming method therefor. <P>SOLUTION: The thermal transfer ink sheet has at least a thermal transfer layer containing a thermally transferable dye and resin on one side of a base film and has a heat-resistant lubricating layer formed on the other side, and a specific sulfosuccinic acid derivative is contained in the thermal transfer layer. The image forming method using the sheet is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermal transfer ink sheet and an image forming method using the same, and more specifically, the present invention relates to a thermal transfer ink sheet and an image forming method for obtaining high-quality prints that are less prone to image defects. It is about.

  Conventionally, various thermal transfer recording methods are known, and among them, the dye diffusion transfer recording method is attracting attention as a process capable of producing a color hard copy closest to the image quality of a silver salt photograph (for example, Non-Patent Document 1 and 2). In addition, it has the advantages of being dry, being able to visualize directly from digital data, and being easy to duplicate, compared to silver salt photography. Furthermore, in response to the recent trend of increasing the printing speed, there is an advantage that the print time for a single sheet is short.

  In this dye diffusion transfer recording system, a thermal transfer ink sheet (hereinafter simply referred to as a thermal transfer sheet or ink sheet) containing a dye and a thermal transfer image receiving sheet (hereinafter also simply referred to as an image receiving sheet) are superimposed. Subsequently, the ink sheet is heated by a thermal head whose heat generation is controlled by an electrical signal, whereby the dye in the ink sheet is transferred to the thermal transfer image-receiving sheet, and image information is recorded. Cyan, magenta, yellow Thus, a color image having a continuous change in color shading can be transferred and recorded by superimposing and recording four colors obtained by adding these three colors or black.

  From this viewpoint of improving color developability, it has been proposed to use various dyes and binder resins (see, for example, Patent Documents 1 to 4). However, due to improved color development and shortened transfer time, other image defects, for example, wrinkles on the ribbon, may cause transfer defects, and blocking (the thermal transfer layer in the thermal transfer ink sheet may peel off from the support). , A phenomenon of adhering to an image receiving sheet) and sticking often occur. As a result, the print defect rate is increased, and as a result, profitability is affected. Further, from the viewpoint of improving profitability, in recent years, the printer processing speed tends to be improved, and it has become important to have passability as the best. Based on this background, studies have been made to change the ink sheet back surface for the purpose of improving sticking (see, for example, Patent Document 5). However, although there is a tendency to further deteriorate by using a high-speed printer, no specific solution has yet been found. Although blocking is also aggravated by speeding up, no solution for materials has been found.

  Blocking occurs because the releasability between the heat-sensitive transfer ink sheet and the heat-sensitive transfer image-receiving sheet is not sufficient, and as a countermeasure, various release agents such as silicone compounds are used as a heat-sensitive transfer ink sheet and / or Alternatively, a method of adding to a thermal transfer image-receiving sheet (see, for example, Patent Document 6) and a method of adding fine particles such as a matting agent to a thermal transfer ink sheet and / or a thermal transfer image-receiving sheet (see, for example, Patent Document 7) have been proposed. ing. However, increasing the amount of these release agents is known to induce the generation of ribbon wrinkles, and it has been difficult to improve blocking without generating ribbon wrinkles.

Japanese Patent Laid-Open No. 7-232482 Japanese Patent Laid-Open No. 5-221116 JP-A-4-357088 JP-A-62-55194 JP-A-8-207461 Japanese Patent Laid-Open No. 9-202058 JP-A-6-40171 “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 “Development of Printer Materials”, issued by CMC Co., Ltd., 1995, p. 180

  An object of the present invention is to provide a thermal transfer ink sheet and an image forming method thereof in which blocking is eliminated without generating ribbon wrinkles and a high-quality print can be obtained.

  As a result of intensive studies, the inventors have not clarified the detailed reason, but ribbon wrinkles can be obtained by incorporating a compound represented by the following general formula (I) in the thermal transfer layer of the thermal transfer ink sheet. It has been found that blocking is eliminated without causing occurrence and high-quality prints can be obtained. The present invention has been made based on such findings.

That is, the said subject was achieved by the following means.
<1> A thermal transfer ink sheet having at least a thermal transfer layer containing a thermally transferable dye and a resin on one surface of a base film, and having a heat-resistant slipping layer formed on the other surface, A thermal transfer ink sheet comprising a compound represented by the following general formula (I) in a thermal transfer layer.

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, provided that the sum of the number of carbon atoms of R ¹ and R ² is 8 to 24. L ¹ is a single bond or Represents a divalent linking group, and M ¹ represents a cation.)
<2> The thermal transfer ink sheet according to <1>, wherein the thermal transfer layer is coated with a solvent.
<3> The thermal transfer ink sheet according to <1> or <2>, wherein the resin is a resin represented by the following general formula (II).

(In the formula, R represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. L, m and n each represent a ratio of each repeating unit, and the total of l, m and n is 100. 1 represents 10 to 100, m represents 0 to 50, and n represents 0 to 50.)
<4> Any one of <1> to <3>, wherein three types of thermal transfer layers of at least yellow, magenta, and cyan are formed on a single support in a surface sequential manner. Thermal transfer ink sheet.
<5> The thermal transfer ink sheet according to any one of <1> to <4>, which has a protective layer capable of thermal transfer.
<6> The thermal transfer ink sheet according to any one of <1> to <5>, at least one dye-receiving layer on a support, and between the receiving layer and the support A thermal transfer image-receiving sheet having hollow polymer particles and at least one heat-insulating layer containing a hydrophilic polymer, and superposing the thermal transfer layer of the thermal transfer ink sheet and the receiving layer of the thermal transfer image-receiving sheet in contact with each other, An image forming method comprising: forming an image by applying thermal energy corresponding to an image signal from a thermal head.
<7> The image forming method according to <6>, wherein in the heat-sensitive transfer image-receiving sheet, at least one hydrophilic polymer contained in the heat insulating layer is gelatin.
<8> After the thermal transfer layer of the thermal transfer ink sheet and the receiving layer of the thermal transfer image receiving sheet are in contact with each other and forming an image by applying thermal energy according to the image signal from the thermal head, the same thermal The image forming method according to <6> or <7>, wherein a protective layer is formed on the image formed by thermal transfer using a head.

  According to the image forming method using the thermal transfer ink sheet of the present invention, blocking is eliminated without generating ribbon wrinkles, and a high-quality print can be obtained.

Hereinafter, the present invention will be described in detail.
1) Thermal Transfer Ink Sheet First, the thermal transfer ink sheet (ink sheet) of the present invention will be described.
A thermal transfer ink sheet used in combination with a thermal transfer image receiving sheet (image receiving sheet), which will be described later, during thermal transfer image formation can be thermally transferred to one surface of a substrate film (hereinafter also simply referred to as a support). It has at least a thermal transfer layer containing a dye (diffusion transfer dye) and a resin, and a heat-resistant slipping layer is formed on the other surface.
The ink sheet of the present invention contains a compound represented by the following general formula (I) in the thermal transfer layer. Below, the compound represented by the following general formula (I) used for this invention is demonstrated in detail.

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, provided that the sum of the number of carbon atoms of R ¹ and R ² is 8 to 24. L ¹ is a single bond or Represents a divalent linking group, and M ¹ represents a cation.)

R ¹ and R ² in the compound represented by the general formula (I) each independently represent a substituted or unsubstituted alkyl group. The alkyl group may be linear, branched or cyclic. Examples of the substituent include an alkyl group, an alkoxy group, and an alkylamino group. Here, when it has these substituents, 1-6 are preferable as for the total carbon number of a substituted alkyl group. The sum of the number of carbon atoms of R ¹ and R ² is 8-24, preferably 12-18.

L ¹ in the compound represented by the general formula (I) represents a single bond or a divalent linking group, among which a single bond or an alkylene group is preferable, and an alkylene group having 1 to 3 carbon atoms is preferable. Further, a methylene group is more preferable. L ¹ is particularly preferably a single bond.

M ¹ in the compound represented by the general formula (I) represents a monovalent cation, among which sodium ion, potassium ion, and ammonium ion are preferable.

The compound represented by the general formula (I) exhibits a blocking inhibitory effect. Accordingly, the compound represented by the general formula (I) may be any layer as long as it is a layer on the thermal transfer layer side in the thermal transfer ink sheet. Examples of such a layer include the layers described later. Among these, it is preferable to contain in the thermal transfer layer.
As the binder resin containing the compound represented by the general formula (I), a resin used in each layer described later on the thermal transfer layer side on the support can be preferably used.
The compound represented by the general formula (I) is preferably contained in an amount of 0.2 to 30% by mass, more preferably 1.0 to 25.0% by mass, most preferably 100% by mass of the binder resin. It is 5.0-20.0 mass%. Moreover, the said compound may be used independently and may be used in combination of multiple.

  Specific examples of the compound represented by the general formula (I) are shown in the following Table 1 (Exemplary compounds P-1 to P-7). The compound represented by the general formula (I) is exemplified by the following examples. It is not limited to.

  The compound represented by the general formula (I) can be synthesized, for example, according to the method described in “New Science of Dispersion / Emulsification and New Development of Applied Technology”, Technos Co., Ltd. (2004). .

Hereinafter, the thermal transfer layer of the ink sheet will be described.
<Thermal transfer layer (dye layer)>
The thermal transfer layer in the heat-sensitive transfer sheet of the present invention contains a dye (preferably a sublimation dye) and a binder resin, and if necessary, organic fine powder or inorganic fine powder, waxes, silicone resin, fluorine-containing organic compound It is also a preferred embodiment of the present invention to use these together.
Below, the dye which can be used for this invention is demonstrated.

(dye)
The dye used in the present invention is not particularly limited as long as it is melted, diffused or sublimated (preferably sublimated) by heat and transferred from the thermal transfer ink sheet to the image receiving sheet, and the dye for the thermal transfer ink sheet As a conventional dye, a known dye or a known dye can be used effectively.
Preferred dyes include, for example, methine series such as diarylmethane series, triarylmethane series, thiazole series, merocyanine, azomethine series represented by indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazolazomethine, imidazoazomethine, and pyridone azomethine. , Xanthene series, oxazine series, dicyanostyrene, cyanomethylene series typified by tricyanostyrene, thiazine series, azine series, acridine series, benzeneazo series, pyridoneazo, thiophenazo, isothiazoleazo, pyrroleazo, pyralazo, imidazoleazo, thiadiazole Azos such as azo, triazole azo, diazo, etc., spiropyrans, indolinospiropyrans, fluorans, rhodamine lactams, naphthoquinones, anthrax Down system, quinophthalone, and the like.

Specific examples include yellow disperse yellow 231, disperse yellow 201, solvent yellow 93, and magenta dyes such as disperse violet 26, disperse thread 60, solvent red 19 and the like, and cyan. Examples of the dye include Solvent Blue 63, Solvent Blue 36, Disperse Blue 354, Disperse Blue 35, and the like. It is of course possible to use suitable dyes other than these exemplified dyes.
It is also possible to arbitrarily combine the dyes of the above-mentioned hues. For example, a black hue can also be obtained by a combination of dyes.

Below, the dye which can be used suitably for this invention is demonstrated in more detail. First, the yellow dye will be described.
In the thermal transfer layer of the ink sheet used in the present invention, a known dye that has been conventionally used can be used as the yellow dye, and among them, any one of the following general formulas (Y1) to (Y4) The pigment | dye represented by these can be included. However, the yellow dye used in the present invention is not limited to these.
First, the dye represented by the following general formula (Y1) will be described.

In the general formula (Y1), R ¹² and R ¹⁴ each independently represent a monovalent substituent, and R ¹¹ and R ¹³ each independently represent a hydrogen atom or a monovalent substituent. The substituents represented here are not particularly limited, but representative examples include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, acyloxy groups, carbamoyl. Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, anilino group and heterocyclic amino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group Sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbo Group, an alkoxycarbonyl group, a carbamoyl group, an aryl- or heterocyclic azo group, and a imide group, each group may further have a substituent.

In the general formula (Y1), R ¹³ and R ¹⁴ may form a ring. Not specifically defined, the atoms forming a ring, as a representative ^{example, -C (R 15) = N} -, - N = C (R 15) -, - C (= O) -C (R 15) An atomic group represented by ═C (R ¹⁶ ) — or —C (═O) —N (R ¹⁵ ) —C (═O) — can be given. Here, R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or a substituent. Examples of substituents, examples given as the substituent of ^{R 11, R 12, R 13} , R 14 can be mentioned.

R ¹² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group or a carbomoyl group, and R ¹⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. . R ¹¹ and R ¹³ are preferably a hydrogen atom or an alkyl group. Each of the above groups may further have a substituent.

In General Formula (Y1), Ar ¹ represents an aryl group or a heterocyclic group, and Ar ¹ is preferably an aryl group. Here, the aryl group may be substituted with a substituent. Examples of the substituent include an alkyloxycarbonyl group, a sulfonyl group, as well as the examples described as the substituents for R ¹¹ , R ¹² , R ¹³ , and R ^14. Group, sulfonylamino group, hydroxy group, nitro group and the like.
A heterocyclic group is also preferable as Ar ¹ . Preferred heterocyclic groups are preferably aromatic heterocyclic groups, more preferably 5- to 6-membered aromatic heterocyclic groups, imidazolyl groups, pyridyl groups, pyrazolyl groups, thiazolyl groups, benzoimidazolyl groups, quinolyl groups, benzoyl groups, Examples include pyrazolyl group, benzothiazolyl group, isothiazolyl group, benzisothiazolyl group, pyridoisothiazolyl group, thiadiazolyl group and the like.

A preferable range of the maximum absorption wavelength of the azo dye represented by the general formula (Y1) used in the present invention is preferably 400 to 480 nm, and more preferably 420 to 460 nm.
Specific examples of these dyes are shown below.

  Next, the dye represented by the following general formula (Y2) will be described.

In General Formula (Y2), R ^A0 represents a substituent, and n represents an integer of 0 to 4. R ^A1 , R ^A2 , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 8 carbon atoms, cycloalkyl group, alkoxy group, alkoxyalkoxy Represents a group, an alkoxysilane group, an acyl group, a carbamoyl group, a sulfamoyl group, a thioalkoxy group, an alkylsulfonyl group, an amino group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted thiophenoxy group. Here, n is preferably 1 or 2, and R ^A0 is preferably an acyl group, an alkoxycarbonyl group, a carbamoyl group or a sulfamoyl group, and more preferably an acyl group or an alkoxycarbonyl group. R ^A1 and R ^A2 are preferably a hydrogen atom or a hydroxyl group, and at least one of them is preferably a hydroxyl group.
Specific examples of these dyes are shown below.

  Next, the dye represented by the following general formula (Y3) will be described.

In general formula (Y3), R ^1A represents an allyl group or an alkyl group, R ^2A represents a substituted or unsubstituted alkyl group or an aryl group, A represents a single bond or a divalent linking group, single _{bond, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 CH 2 OCH 2 - is. R ^3A represents a hydrogen atom or an alkyl group. Each of these groups may further have a substituent.
Specific examples of these dyes are shown below.

  Next, the dye represented by the following general formula (Y4) will be described.

In general formula (Y4), R ^{1B to} R ^4B each independently represent a hydrogen atom or a substituent.

  The dye represented by any one of the general formulas (Y1), (Y2), (Y3) or (Y4) can be synthesized by a known method.

Next, the magenta dye will be described.
In the thermal transfer layer of the ink sheet used in the present invention, known dyes that have been conventionally used can be used as magenta dyes. Among them, the following general formulas (M1) to (M4) are used. Can be suitably used. However, the magenta dye used in the present invention is not limited to these.
First, the dye represented by the following general formula (M1) will be described.

In the general formula (M1), D ^{1 to} D ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxy group. carbonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, D ⁶ and D ⁷ each independently represent a hydrogen atom, an alkyl group, an alkyl cyano group or Represents an aryl group. D ⁶ and D ⁷ may be bonded to each other to form a ring, or D ³ and D ⁶ or / and D ⁵ and D ⁷ may be bonded to each other to form a ring. X, Y and Z represent ═C (D ⁸ ) — or a nitrogen atom. Here, D ⁸ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group. When X and Y are = C (D ⁸ )-, or when Y and Z are = C (D ⁸ )-, two D ⁸ are bonded to each other to form a saturated or unsaturated carbocyclic ring. Also good. Each of these groups may further have a substituent.

  Among the compounds represented by the general formula (M1), a compound represented by the following general formula (M1B) is preferable.

In the general formula (M1B), D ^{19 to} D ²³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxy group. A carbonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or an amino group is represented. D ^{19 to} D ²³ have the same meanings as D ^{1 to} D ⁵ in the general formula (M1), respectively, and the preferred ranges are also the same.
D ²⁴ and D ²⁵ each independently represents a hydrogen atom, an alkyl group, an alkylcyano group or an aryl group. D ²⁴ and D ²⁵ may be bonded to each other to form a ring, and D ²¹ and D ²⁴ may be bonded to each other and / or D ²³ and D ²⁵ may be bonded to each other to form a ring. D ²⁴ and D ²⁵ are synonymous with D ⁶ and D ⁷ in the general formula (M1), respectively, and preferred ranges thereof are also the same.
D ²⁶ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group. D ²⁶ has the same meaning as D ⁸ in formula (M1), and the preferred range is also the same.
Each of these groups may further have a substituent.
Specific examples of the dye represented by the general formula (M1) are shown below.

  Next, the compound represented by the following general formula (M2) will be described in detail.

In general formula (M2), A represents a heterocyclic group which may have a substituent, wherein the heterocyclic ring is selected from the group consisting of imidazole, pyrazole, thiazole, benzothiazole, isothiazole, benzoisothiazole and thiophene. To express. A is preferably an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzothiazolyl group, an isothiazolyl group, a benzisothiazolyl group, or a thienyl group, and among them, an imidazolyl group is preferable. Each of these groups may have a substituent.
Examples of the substituent which the heterocyclic group in A may be substituted include cyano group, thiocyano group, nitro group, halogen atom, alkyl group, alkoxy group, formyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, alkylcarbonyl Among them, a cyano group, a thiocyano group, a cyanomethyl group, a nitro group, and an alkyl group are preferable substituents.
E represents an aminophenyl group, a tetrahydroquinolinyl group, a euroridyl group or an aminoquinolinyl group which may have a substituent. The amino in the aminophenyl group and aminoquinolinyl group includes an amino group and a substituted amino group, and examples of the substituent include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an amide group, and a heterocyclic group. Is mentioned.
E is preferably an aminophenyl group substituted with an alkyl group or an amide group.
Specific examples of the dye represented by the general formula (M2) are shown below.

  Next, the compounds represented by the following general formula (M3) and general formula (M4) will be described in detail.

In the general formula (M3), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent, and R ⁷² and R ⁷⁴ each independently represent a substituent. n11 represents an integer of 0 to 4. n12 represents the integer of 0-2. Here, when n11 represents an integer of 2 to 4 or n12 represents 2, a plurality of R ⁷⁴ or a plurality of R ⁷² may be the same or different. Examples of the substituent in R ^{71 to} R ⁷⁴ include a halogen atom, an alkyl group (including a cycloalkyl group (any number of rings)), an alkenyl group (including a cycloalkenyl group (any number of rings)), and an alkynyl group. , Aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group), acylamino group Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryls Examples thereof include a sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, and an imide group, and each group may further have a substituent.

Examples of R ⁷¹ and R ⁷³ include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, A hydrogen atom or a substituted or unsubstituted alkyl group is preferable, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is more preferable, and a hydrogen atom is more preferable.

Examples of R ⁷² and R ⁷⁴ are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl Group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, preferably alkoxy group, A oxyoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group, more preferably an alkoxy group and an aryloxy group. Each group may have a substituent.

In the general formula (M4), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. n13 represents an integer of 0 to 4, and n14 represents an integer of 0 to 2. Here, when n13 represents an integer of 2 to 4 or n14 represents 2, the plurality of R ⁸⁴ or the plurality of R ⁸² may be the same or different. ^Examples of the substituent in R ⁸¹ , R ⁸² and R ⁸⁴ include those described for R ^{71 to} R ⁷⁴ described above.

Examples of R ⁸¹ include substituents as described for R ⁷¹ and R ⁷³ , and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, it is a hydrogen atom.

Examples of R ⁸² and R ⁸⁴ include substituents as described for R ⁷² and R ⁷⁴ . An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group are preferable, and an alkoxy group and an aryloxy group are more preferable. Each group may have a substituent.

  Regarding the preferred combination of substituents of the dye represented by the general formula (M3) or the general formula (M4), a compound in which at least one of various substituents is the preferred group is preferable, and more various A compound in which the substituent is the preferred group is more preferable, and a compound in which all the substituents are the preferred group is most preferable.

Specifically, examples of preferable combinations of substituents in the general formula (M3) are R ⁷¹ is a hydrogen atom, R ⁷² is an aryloxy group, R ⁷³ is a hydrogen atom, n11 is 0, and n12 is an integer of 0 to 2. It is a combination. A more preferable combination is a combination in which R ⁷¹ is a hydrogen atom, R ⁷² is an aryloxy group, R ⁷³ is a hydrogen atom, n11 is 0, and n12 is 2.
Specifically, a preferable combination example of substituents in the general formula (M4) is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1 or 2, and n14 is 0. A more preferable combination is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1, and n14 is 0. A more preferred combination is a combination in which R ⁸¹ is a hydrogen atom, R ⁸² is an aryloxy group, n13 is 1, n14 is 0, and R ⁸² is substituted at the o-position with respect to the amino group.
Specific examples of these dyes are shown below.

  The compounds represented by the general formulas (M1) to (M4) can be synthesized by a known method.

Next, the cyan dye will be described.
In the thermal transfer layer of the ink sheet used in the present invention, a known dye that has been conventionally used can be used as a cyan dye. Can be suitably used. However, the cyan dye used in the present invention is not limited to these dyes.
First, the dye represented by the following general formula (C1) will be described.

In general formula (C1), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. n18 represents an integer of 0 to 4, and n19 represents an integer of 0 to 2. Here, when or where n19 when n18 represents an integer of 2 to 4 represents 2, a plurality of R ¹¹⁴ or R ¹¹² may be the same or different from each other. Examples of the substituent in R ^{111 to} R ¹¹⁴ include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a formyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, Aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl or aryl Sulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, etc. And the like.

Examples of R ¹¹¹ and R ¹¹³ include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group.

Examples of R ¹¹² and R ¹¹⁴ are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl Group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably hydrogen atom, Gen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably a halogen atom, a substituted or unsubstituted alkyl group, substituted or An unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group.
Specific examples of the dye represented by the general formula (C1) are shown below.

Among the dyes represented by the general formula (C1), those not commercially available are disclosed in U.S. Pat. Nos. 4,757,046, 3,770,370, DE 2316755, JP, 2004-51873, JP-A-7-137455, JP-A-61-31292, and J.P. Chem. Soc. Perkin transfer I, 2047 (1977), by Champan, “Merocyanine Dye-Doner Element Used in Thermal Dye Transfer”.
Next, the dye represented by the following general formula (C2) will be described in detail.

In the general formula (C2), D ^{14 to} D ²¹ are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonyl. It represents an amino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and D ²² and D ²³ each independently represent a hydrogen atom, an alkyl group or an aryl group. D ²² and D ²³ may be bonded to each other to form a ring, or D ¹⁹ and D ²² or / and D ²⁰ and D ²³ may be bonded to each other to form a ring.
D ¹⁴ is preferably an acylamino group, a ureido group and an alkoxycarbonyl group, more preferably an acylamino group and a ureido group, still more preferably an acylamino group, and most preferably a group represented by the following general formula (IV).

In the formula, D ²⁴ is an alkyl group (preferably having a carbon number of 1 to 12, such as methyl, ethyl, isopropyl, n-propyl, t-butyl, etc.), an aryl group (preferably having a carbon number of 6 to 10, such as phenyl, m-nitrophenyl, p-nitrophenyl, p-tolyl, p-methoxyphenyl, naphthyl, m-chlorophenyl, p-chlorophenyl, etc.) or a heterocyclic group (preferably having 0 to 10 carbon atoms, oxygen atom, nitrogen atom or A 5- to 8-membered heterocyclic group containing any of the sulfur atoms as a ring constituent atom, for example, pyridyl, furyl, tetrahydrofuryl, etc.), preferably a heterocyclic group or an alkyl group, more preferably a pyridyl group , Furyl group, tetrahydrofuryl group or methyl group.

D ¹⁵ , D ¹⁶ and D ^{18 to} D ²¹ are preferably a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 12, such as methyl, ethyl, isopropyl, n-propyl, t-butyl, etc.). More preferably, they are a hydrogen atom, a methyl group, and an ethyl group. D ¹⁷ is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, t-butyl, etc.), a halogen atom, a cyano group, a nitro group, a heterocyclic ring. It is a group. More preferably, they are a hydrogen atom and a halogen atom. D ¹⁶ and D ¹⁷ may be bonded to each other to form a ring. D ²² and D ²³ are preferably a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 12, such as methyl, ethyl, isopropyl, n-propyl, t-butyl, etc.), more preferably a methyl group or ethyl. Group, n-propyl group. These alkyl groups may be further substituted with other substituents. When the alkyl group is substituted, preferred substituents are a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an amino group, an acyl group, an acyloxy group, an acylamino group, an alkylthio group, an arylthio group, a sulfonylamino group, A sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, more preferably a carbamoyl group. D ²² and D ²³ are more preferably a hydrogen atom, a methyl group, or an ethyl group.
Specific examples of the dye represented by the general formula (C2) are shown below.

  The dye represented by the general formula (C2) can be synthesized by a known method.

(Binder resin)
As the binder resin contained in the thermal transfer layer for carrying the dye as described above, various types are known, and these can be used in the present invention. Examples include modified cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose nitrate, polyvinyl alcohol, polyvinyl acetate , Polyvinyl resins such as polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, polystyrene, polyvinyl chloride, acrylic resins such as polyacrylonitrile, polyacrylate, polyacrylamide, polyurethane resins, polyamide resins, polyester resins, polycarbonate resins, phenoxy resins , Phenol resin, epoxy resin, various elastomers, etc. It is possible to have. In addition to using these alone, it is also possible to use them by mixing or in the case of polymers, copolymerizing each constituent monomer. Crosslinking with various crosslinking agents is also a preferred embodiment.
Among these, modified cellulose resins and vinyl resins are preferably used, and propionic acid modified celluloses, polyvinyl butyral, and polyvinyl acetal can be more preferably used.

  Moreover, it is preferable to use resin represented by the following general formula (II) as said binder resin.

In general formula (II), R represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. l, m, and n represent the ratio of each repeating unit. When the total of l, m, and n is 100, l is 10-100, m is 0-50, and n is 0-50.
R is preferably an unsubstituted alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
l is preferably 30 to 95, more preferably 50 to 90. m is preferably from 0 to 30, and more preferably from 1 to 20. n is preferably 1 to 40 and more preferably 5 to 30.
The resin represented by the general formula (II) preferably has an average molecular weight of 1,000 to 100,000, more preferably 5,000 to 50,000.
The resin represented by the general formula (II) may be a block copolymer or a random copolymer, and can be synthesized by any copolymerization method.
As these resins, commercially available resins can be used. For example, Denkabutyral # 6000-C (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.), Denkabutyral # 5000-A (trade name, Electrochemical) Kogyo Co., Ltd.) and Eslex KS-1 (trade name, manufactured by Sekisui Chemical Co., Ltd.).

  The binder resin is preferably contained in an amount of 30 to 70% by mass, more preferably 40 to 60% by mass, based on the entire thermal transfer layer of the thermal transfer ink sheet of the present invention.

(solvent)
A dye ink is prepared by dissolving or dispersing the sublimable dye and the binder resin in a solvent, and various known solvents can be used as the solvent used in this case. Examples include alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; water. These solvents may be used alone or in combination.

(Additive)
In addition to the dye, the binder resin, and the compound represented by the general formula (I), the dye layer has a variety of properties for the purpose of improving various performances such as storage stability, runnability in the printer, and peelability after printing. Additives can be added. As typical additives, organic or inorganic fine particles and waxes are preferably used.

Examples of organic fine particles include polyolefin resins such as polyethylene and polypropylene, polyamide resins such as fluororesin and nylon resin, urethane resins, styrene / acrylic cross-linked resins, phenol resins, urea resins, melamine resins, polyimide resins, benzoguanamine resins, and the like. These fine particles can be suitably used, and polyethylene fine particles are more preferably used. Moreover, as inorganic fine particles, fine particles such as calcium carbonate, silica, clay, talc, titanium oxide, magnesium hydroxide, and zinc oxide can be preferably used.
The organic or inorganic fine particles are preferably contained in the range of 0.5 to 5% by mass with respect to the binder resin of the thermal transfer layer.

  In addition to the above-described sublimable dye, binder resin, and organic or inorganic fine particles, it is also a preferred embodiment to contain a wax in the thermal transfer layer. Usable waxes include petroleum-derived waxes such as microcrystalline wax and paraffin wax; mineral-derived waxes such as montan wax; plant-derived waxes such as carnauba wax, tree wax and candelilla wax; beeswax, whale wax, ibota wax, shellac Animal-derived waxes such as waxes; Fischer-Tropsch waxes, various low molecular weight polyethylenes, fatty acid esters, fatty acid amides, synthetic waxes such as silicone waxes and partially modified waxes are preferably used.

  Another preferred embodiment includes the inclusion of resins such as silicone resin, fluororesin, acrylic resin, cellulose resin, vinyl chloride-vinyl acetate copolymer, and nitrified cotton. Such waxes and resins can be contained in the range of 0.1 to 10% by mass, preferably 1 to 3% by mass with respect to the total solid content in the state formed as the thermal transfer layer.

Next, the configuration of the thermal transfer ink sheet of the present invention will be described.
The thermal transfer ink sheet of the present invention is a thermal transfer ink sheet in which a thermal transfer layer of at least one color is provided on one surface of a support, and the thermal transfer layer is an application containing the dye and resin of the thermal transfer layer. It is formed by applying a liquid.

<Support>
Any conventionally known support may be used as long as it has the required heat resistance and strength. Examples include thin papers such as glassine paper, condenser paper, puffin paper, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyetherketone, polyethersulfone, and other highly heat-resistant polyesters, polypropylene, polycarbonate, Specific examples of supports in which cellulose acetate, polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, ionomer, and other plastic stretched or unstretched films, and laminates of these materials are preferred As mentioned. Among these, the polyester film is particularly preferable, and a stretched polyester film is most preferable. The thickness of the support is appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but a thickness of about 1 to 100 μm is preferably used. More preferably, it is about 2-50 micrometers, More preferably, about 3-10 micrometers is used.

In the sublimation type thermal transfer recording method, it is necessary to transfer only the dye of each hue contained in the thermal transfer ink sheet at the time of printing, and transfer of the resin carrying the dye is not preferable. For this purpose, the adhesion between the thermal transfer layer of the thermal transfer ink sheet and the support must be strong. If this adhesion is weak, the thermal transfer layer itself adheres to the image receiving sheet and the image quality of the print is impaired.
However, in the case of the polyester film described above as an example of a suitable support, it cannot be said that the wettability of the ink of each hue described later is good, and the adhesive force may be insufficient. In order to cope with this, a method of treating the support surface by physical means and / or a method of forming an easy-adhesion layer is preferably used.

It is preferable that an easy-adhesion layer made of a resin is formed on a support and a dye layer is provided thereon. In order to form an easy-adhesion layer, urethane resin, polyester resin, polypropylene resin, polyol resin, acrylic resin, and a reaction product of these resins with isocyanates can be used. Examples of isocyanates include conventionally used diisocyanate compounds and triisocyanate compounds. The coating amount is preferably 0.05 to 0.1 g / m ² .
In producing the heat-sensitive transfer ink sheet, it is possible to use a support provided with an easy-adhesion layer in advance and form a heat-transfer layer thereon.

(Coating method of thermal transfer layer)
The thermal transfer layer in the thermal transfer ink sheet of the present invention is preferably coated on a support by applying a solvent. Specifically, the thermal transfer layer in the thermal transfer ink sheet of the present invention is formed by applying a coating liquid (ink) for the thermal transfer layer on a support by a gravure printing method or other forming means and drying it. The dye layer ink is obtained by dissolving or dispersing a sublimable dye, a binder resin, and other additives such as organic or inorganic fine particles and wax, if necessary, in an appropriate solvent.
The thickness of the thermal transfer layer is preferably about 0.2 to 5 g / m ² in a dry state, more preferably about 0.4 to ² g / m ² . The sublimation dye content in the thermal transfer layer is preferably 5 to 90% by mass, more preferably about 10 to 70% by mass.

  A preferred embodiment of the thermal transfer ink sheet of the present invention is shown in FIGS. FIGS. 1A to 1C are plan views of a thermal transfer ink sheet in which dye layers of respective hues are formed in surface order. 2D to 2G are plan views of a thermal transfer ink sheet in which an ink layer (dye layer) is formed on a separate support. FIG. 3 is a cross-sectional view showing a preferred embodiment of the thermal transfer ink sheet of the present invention.

Although the thermal transfer ink sheet of the present invention has a dye layer that is a thermal transfer layer of at least one color, the thermal transfer ink sheet is generally printed in order of yellow, magenta, and cyan. As shown in FIG. 1 (a), it is preferable to provide a dye layer of each hue in the order of a yellow dye layer Y, a magenta dye layer M, and a cyan dye layer C on the same support. Further, a black layer BK may be provided as shown in FIG. Furthermore, a transferable protective layer laminate 4 described later may be provided as shown in FIG. However, the arrangement of the dye layer which is the thermal transfer layer of each hue in the present invention is not limited to these, and can be arbitrarily arranged as necessary.
In addition, since the peelability between the heat-sensitive transfer ink sheet and the image receiving sheet changes depending on the order of printing, it is also a preferable aspect to change the content of the additive depending on each dye layer. For example, the content of the release agent can be increased as the dye layer is printed later.

  In addition, as shown in FIG. 2, instead of providing each hue layer on the same support, it is also possible to form each hue dye layer on a separate support.

In the thermal transfer ink sheet of the present invention, the dye layer and the protective layer may have a single layer structure, or may have a two-layer structure or a multilayer structure of three or more layers. In addition, in the dye layer of each hue, a single layer structure and a multilayer structure may be mixed. The configuration shown in FIG. 3 is an example of such a case. In FIG. 3, the yellow dye layer Y, the magenta dye layer M, and the cyan dye layer C have a single layer structure, and a release layer 4a, a protective layer 4b, and an adhesive that constitute a transferable protective layer laminate 4 described later. The layer 4c has a multilayer structure.
Yes.

Dye layer total thickness of the multilayer structure is preferably about 0.2-5 g / m ^2, about 0.4~2g / m ² is more preferred.
The thickness of one layer constituting the dye layer is preferably about 0.2 to ² g / m ² . The sublimable dye contained in the entire dye layer is preferably about 5 to 90% by mass, more preferably about 10 to 70% by mass.

<Transferable protective layer laminate>
In the present invention, it is also a preferred embodiment to provide a transferable protective layer laminate on the thermal transfer ink sheet. The transferable protective layer laminate is for forming a protective layer made of a transparent resin on the heat-transferred image by thermal transfer to cover and protect the image. Durability such as scratch resistance, light resistance, weather resistance, etc. Used to improve the performance. If the dye transferred on the image receiving sheet is exposed to the surface, the image durability such as light resistance, scratch resistance, chemical resistance, etc. may be insufficient, and such a transparent protective layer should be provided. Is preferred.
As illustrated in FIG. 3, the release layer 4a, the protective layer 4b, and the adhesive layer 4c can be formed in this order on the support from the support side. It is also possible to form the protective layer with a plurality of layers. When the protective layer has the functions of other layers, the release layer and the adhesive layer can be omitted. As the support, a support provided with an easy-adhesion layer can also be used.

  As the resin for forming the protective layer, a resin excellent in scratch resistance, chemical resistance, transparency and hardness is preferable. Polyester resin, polystyrene resin, acrylic resin, polyurethane resin, acrylic urethane resin, silicone modification of each of these resins Examples thereof include resins, mixtures of these resins, ionizing radiation curable resins, ultraviolet blocking resins, and the like. In addition, various resins conventionally known as protective layer forming resins can be used. In addition, UV absorbers, antioxidants, fluorescent brighteners, organic fillers, and / or inorganic fillers may be added as necessary for the purpose of imparting UV absorption, film breakage during transfer, gloss, whiteness improvement, etc. It is also preferable to add appropriately.

  As the acrylic resin that can be used in the present invention, a polymer comprising at least one monomer selected from conventionally known acrylate monomers and methacrylate monomers is preferable. In addition to the acrylic monomer, styrene, acrylonitrile, and the like are used together. It may be polymerized. A preferred monomer is methyl methacrylate, which is preferably contained in an amount of 50% by mass or more based on the total amount of raw material monomers.

  As the polyester resin that can be used in the present invention, a conventionally known saturated polyester resin can be used. Examples of the acid component of the polyester resin used in the present invention include terephthalic acid, isophthalic acid, and orthophthalic acid as aromatics. 2,6-naphthalenedicarboxylic acid tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid and the like. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid, tricyclodecane dicarboxylic acid, decalin dicarboxylic acid, and the like. These compounds may be methyl esterified or may be acid anhydrides thereof. .

  Furthermore, p- (hydroxyethoxy) benzoic acid, hydroxypivalic acid, γ-butyryllactone, ε-caprolactone, fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like can be used in combination. . Further, if necessary, a tri- or higher functional polycarboxylic acid such as trimellitic acid, pyromellitic acid or the like and tetracarboxylic acid may be used if it is 10 mol% or less based on the total carboxylic acid component. I can do it. In particular, a structure in which one or more acid components in which a part of an aromatic dicarboxylic acid is substituted with sulfonic acid or a salt thereof is included in one molecular chain, and the upper limit of the amount of these sulfonic acid substitutions (or groups of the salts) is preferable. For example, it is more preferable that it is copolymerized within a range soluble in an organic solvent in that it can be used by mixing with other organic solvent-soluble additives and resins. Preferred aromatic dicarboxylic acids containing these sulfonic acid substitutions (or salts thereof) include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, Examples thereof include 5 (4-sulfophenoxy) isophthalic acid and the like, ammonium salts thereof, and metal salts thereof such as lithium, potassium, magnesium, calcium, copper and iron. Particularly preferred is 5-sodium sulfoisophthalic acid.

  Examples of the polyol component that is another raw material of the polyester that can be used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1 , 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, hydroxypivalic acid neopentyl glycol ester, di Examples include methylol heptane and 2,2,4-trimethyl-1,3-pentanediol. Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, neopentyl glycol propylene oxide adduct may be used as necessary.

  As aromatic-containing glycols, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct of bisphenol A and propylene Examples thereof include glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols such as oxide adducts. Examples of the alicyclic diol component include tricyclodecane diol, tricyclodecane dimethylol, tricyclodecane dimethanol (TCD-M), cyclohexane diol, 1,4-cyclohexane dimethanol, hydrogenated bisphenol A, and hydrogenation. Examples thereof include ethylene oxide and propylene oxide adducts of bisphenol A. The polyester resin has a glass transition temperature of preferably 50 to 120 ° C., a molecular weight of preferably 2,000 to 40,000, and a range of 4,000 to 20,000 in which the foil breaks during transfer of the protective layer. Is better and more preferable.

  By using the ionizing radiation curable resin, a protective layer having particularly excellent plasticizer resistance and scratch resistance can be obtained. As a specific example, there is one in which a radical polymerizable polymer or oligomer is crosslinked and cured by irradiation with ionizing radiation. At this time, if necessary, a photopolymerization initiator may be added and polymerized and cross-linked by an electron beam or ultraviolet rays. In addition, a known ionizing radiation curable resin can be used.

  In order to impart light resistance to the printed matter, a protective layer containing an ultraviolet absorber and / or an ultraviolet blocking resin is also a preferred embodiment.

  Depending on the characteristics of the dye used for image formation, these UV absorbers can be used in combination with different ones so as to cover the effective UV absorption wavelength range. It is preferable to use a mixture of a plurality of different structures so as not to precipitate.

Examples of organic fillers and / or inorganic fillers include polyethylene wax, bisamide, nylon, acrylic resin, cross-linked polystyrene, silicone resin, silicone rubber, talc, calcium carbonate, titanium oxide, alumina, microsilica, colloidal silica, and other fine silica particles. It can be illustrated. In the heat-sensitive transfer ink sheet of the present invention, known materials can be suitably used without being limited thereto.
The organic filler and / or the inorganic filler preferably have a particle size of 10 μm or less, preferably in the range of 0.1 to 3 μm, good slipperiness and high transparency. The addition amount of the filler is preferably such that the transparency is maintained when transferred, and is preferably in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the resin.

  The protective layer depends on the kind of the resin for forming the protective layer, but is formed by a method similar to the method for forming the thermal transfer layer, and a thickness of about 0.5 to 10 μm is preferable.

<Release layer>
In the case where the protective layer is difficult to peel off from the support during transfer, it is also a preferred embodiment to form the release layer 4a between the support and the protective layer. The release layer is made of a material having excellent releasability such as waxes, silicone wax, silicone resin, fluorine resin, or a resin having a relatively high softening point that does not melt by the heat of the thermal head, for example, a cellulose resin. Conventionally, a coating liquid comprising an acrylic resin, a polyurethane resin, a polyvinyl acetal resin, an acrylic vinyl ether resin, a maleic anhydride resin, a silicone resin, a fluororesin, or a resin containing a heat release agent such as wax in these resins is used. It can form by apply | coating and drying by methods, such as a well-known gravure coat and a gravure reverse coat. Among the above resins, as the acrylic resin, a resin copolymerized with a simple substance such as acrylic acid or methacrylic acid or other monomers is preferable, and excellent in adhesion to the support and releasability from the protective layer. Yes. These resins may be used alone or in combination.
This release layer remains on the support side during printing (transfer).
The thickness of the layer is preferably about 0.5 to 5 μm. Matte the surface of the release layer by incorporating various particles in the release layer or by matting the surface of the release layer on the protective layer side so that the surface of the image receiving sheet after printing is matte Is also possible.

  A release layer may be formed between the transferable protective layer 4b and the release layer 4a. The release layer is transferred together with the protective layer. After transfer, it is the uppermost layer of the printed image-receiving sheet, and is formed from a resin having excellent transparency, abrasion resistance, and chemical resistance. Examples of the resin include an acrylic resin, an epoxy resin, a polyester resin, and a styrene resin. It is also possible to add fillers, waxes and the like.

<Adhesive layer>
It is preferable to provide an adhesive layer 4c as the uppermost layer of the transferable protective layer laminate 4 on the protective layer 4b. Thereby, the transferability of the protective layer can be improved. Known adhesives, heat-sensitive adhesives, and thermoplastic resins can be used for the adhesive layer. Examples include polyester resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, and acrylic-ultraviolet absorbers. Examples thereof include resins having good adhesiveness during heating, such as copolymer resins, ultraviolet absorbing resins, butyral resins, epoxy resins, polyamide resins, vinyl chloride resins, and polycarbonate resins. Among these, a thermoplastic resin having a glass transition temperature (Tg) of 40 ° C to 80 ° C is preferable.
When Tg is less than 40 ° C., the adhesion between the image to be coated and the transparent protective layer tends to be insufficient. When Tg is 80 ° C. or higher, the transferability of the transparent protective layer tends to be insufficient.
Particularly preferred are polyvinyl chloride resins, polyvinyl acetate resins, and vinyl chloride / vinyl acetate copolymer resins having a degree of polymerization of 50 to 300, more preferably 50 to 250.
As the ultraviolet absorbing resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber to a thermoplastic resin or an ionizing radiation curable resin can be used.

  The below-mentioned ultraviolet absorber can be added to the adhesive layer. Further, as an additive, a coloring pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent whitening agent, and the like can be used as necessary. By applying and drying a resin that constitutes the adhesive layer as described above and, if necessary, a coating liquid to which the above additives are added, a thickness of preferably about 0.5 to 10 μm in a dry state. To form an adhesive layer. Preferably it is 0.5-5 micrometers, More preferably, it is 0.5-3 micrometers.

(UV absorber)
The ultraviolet absorber preferably has absorption in the ultraviolet region and does not have an absorption edge in the visible region. Specifically, when it is added to the layer to be added to form a heat-sensitive transfer ink sheet (when used for a heat-sensitive transfer image-receiving sheet), it has a maximum absorption in the range of 330 nm to 370 nm. The absorption concentration is preferably Abs 0.8 or more, more preferably the absorption concentration at 380 nm is Abs 0.5 or more. Moreover, it is preferable that the absorption density of 400 nm is Abs0.1 or less. In addition, when the absorption density in the range exceeding 400 nm is high, the obtained image is yellowed, which is not preferable.
As such an ultraviolet absorber, conventionally known inorganic ultraviolet absorbers and organic ultraviolet absorbers can be used. Organic UV absorbers include salicylates, benzophenones, benzotriazoles, triazines, substituted acrylonitriles, nickel chelates, hindered amines, and other non-reactive UV absorbers, and their non-reactive UV absorption For example, an addition polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group, or an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, or the like is introduced into the agent. A copolymerized or grafted plastic resin can be used as the ultraviolet blocking resin. Among these ultraviolet absorbers, organic ultraviolet absorbers described later, particularly benzophenone, benzotriazole, and triazine are preferable.
In addition, a method of obtaining an ultraviolet blocking resin by dissolving an ultraviolet absorbent in a monomer or oligomer of a resin used for a protective layer and then polymerizing the monomer or oligomer is also disclosed (Japanese Patent Application Laid-Open No. 2006-21333). Issue gazette). In this case, the ultraviolet absorber may be non-reactive.
Commercially available UV absorbers include Tinuvin-P (manufactured by Ciba Geigy), JF-77 (manufactured by Johoku Chemical), Sea Soap 701 (manufactured by Shiraishi Calcium), Sumisop 200 (manufactured by Sumitomo Chemical), and Biosoap 520 (manufactured by Kyodo Yakuhin). And Adeka Stub LA-32 (manufactured by Asahi Denka) (all are trade names).

  In the present invention, the ultraviolet absorber may have a high molecular weight. In this case, a mass average molecular weight of 10,000 or more is preferable, and a mass average molecular weight of 100,000 or more is more preferable. As a means for increasing the molecular weight, it is preferable to graft an ultraviolet absorber onto the polymer. The polymer that becomes the main chain preferably has a polymer skeleton that is inferior in dyeability to the dye used in combination. Moreover, it is preferable to have sufficient film strength when the film is formed. The graft ratio of the ultraviolet absorber to the polymer main chain is preferably 5 to 20% by mass, and more preferably 8 to 15% by mass.

Moreover, the polymer containing the unit (ultraviolet absorber unit) having ultraviolet absorbing ability may be a latex. In this case, by forming a latex, it becomes possible to form a receptor layer by coating an aqueous dispersion coating solution to reduce the manufacturing cost. As a method for forming a latex, for example, a method described in Japanese Patent No. 3450339 can be used. Examples of the ultraviolet absorber made into latex include, for example, ULS-700, ULS-1700, ULS-1383MA, ULS-1635MH, XL-7016, ULS-933LP, ULS-935LH, Shin-Nakamura Chemical Co., Ltd. Commercially available ultraviolet absorbers such as New Coat UVA-1025W, New Coat UVA-204W, and New Coat UVA-4512M (both are trade names) can also be used.
When latex containing a unit having a UV-absorbing unit is made into a latex, the above-mentioned dyeable receiving polymer is also made into a latex in the same manner, and after mixing both, the receiving layer in which the UV absorber is uniformly dispersed is formed. Can be formed.

  The addition amount of the polymer containing the unit having ultraviolet absorbing ability or the latex thereof is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to the dyeable receiving polymer or the latex forming the receptor layer.

The ultraviolet absorber may be an organic compound or an inorganic compound.
In the case of organic ultraviolet absorbers, those represented by any one of the following general formulas (1) to (8) are preferred.

^{Wherein, R 11, R 12, R} 13, R 14, R 15 are, each independently, a hydrogen atom, a halogen atom, an alkyl group (cycloalkyl group, including a bicycloalkyl group), an alkenyl group (cycloalkenyl group, (Including bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups , Alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino Group, mercap Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or hetero It represents a ring azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, or a silyl group.

In the formula, R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), or an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl Oxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group , Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide Represents a group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, or a silyl group. T represents an aryl group, a heterocyclic ring, or an aryloxy group. Preferably T is an aryl group.

In the formula, X ³¹ , Y ³¹ and Z ³¹ each independently represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or heterocyclic group. However, at least one of X ³¹ , Y ³¹ and Z ³¹ represents a group represented by the general formula (a).

In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), or an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl Oxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group , Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, It represents an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, or a silyl group. Further, adjacent R ³¹ and R ³² may be linked to form a ring.

In the formula, R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), or an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl Oxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group , Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide Represents a group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, or a silyl group.

In the formula, Q represents an aryl group or a 5- or 6-membered heterocycle, R ⁵¹ represents a hydrogen atom or an alkyl group, and X ⁵¹ and Y ⁵¹ each independently represent a cyano group, —COOR ⁵² , —CONR ⁵² R ⁵³ , —COR ⁵² , —SO ₂ OR ⁵² , —SO ₂ NR ⁵² R ⁵³ , each of R ⁵² and R ⁵³ independently represents a hydrogen atom, an alkyl group, or an aryl group. One of R ⁵² and R ⁵³ is preferably a hydrogen atom. X ⁵¹ and Y ⁵¹ may be linked to form a 5- or 6-membered ring. When X ⁵¹ and Y ⁵¹ are a carboxyl group, they may be in a salt form.

In the formula, each of R ⁶¹ and R ⁶² independently represents a hydrogen atom, an alkyl group, an aryl group, or a group of nonmetallic atoms necessary to form a 5- or 6-membered ring by connecting to each other. Further, either R ⁶¹ or R ⁶² may be bonded to the methine group adjacent to the nitrogen atom to form a 5- or 6-membered ring. X ⁶¹ and Y ⁶¹ may be the same or different and have the same ^meanings as X ⁵¹ and Y ⁵¹ in formula (5).

In the formula, R ^{71 to} R ⁷⁴ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group, and R ⁷¹ and R ⁷⁴ together form a double bond. When R ⁷¹ and R ⁷⁴ are combined to form a double bond, R ⁷² and R ⁷³ may be linked to form a benzene ring or a naphthalene ring. R ⁷⁵ represents an alkyl group or an aryl group, Z ⁷¹ represents an oxygen atom, a sulfur atom, a methylene group, an ethylene group,> N—R ⁷⁶ or> C (R ⁷⁷ ) (R ⁷⁸ ), and R ⁷⁶ represents an alkyl group Represents an aryl group, and R ⁷⁷ and R ⁷⁸ may be the same or different and each represents a hydrogen atom or an alkyl group. X ⁷¹ and Y ⁷¹ may be the same or different and have the same ^meanings as X ⁵¹ and Y ⁵¹ in formula (5). n represents 0 or 1.

In the formula, each of R ^{81 to} R ⁸⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Amino groups (including anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, mercapto groups, alkylthio groups, Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, or silyl group, R ⁸⁷ and R ⁸⁸ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group, R ⁸⁷ and R ⁸⁸ may be linked to form a 5- or 6-membered ring.

  In the general formulas (1) to (8) and the general formula (a), each substituent (for example, a group having an alkyl part, an aryl part, or a heterocyclic part) may be substituted with the following substituents. . In addition, examples of the groups in the general formulas (1) to (8) and the general formula (a) and specific groups are exemplified by corresponding groups among the groups shown below.

Such groups are described and exemplified below.
Halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [represents a linear, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3-yl group), It is intended to encompass such tricyclo structure having many cyclic structures into. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (preferably a carbon number of 3 A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group and 2-cyclohexene -1-yl group), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a hydrogen atom of a bicycloalkene having one double bond. A monovalent group, for example, a bicyclo [2,2,1] hept-2-en-1-yl group, It is intended to include cyclo [2,2,2] oct-2-en-4-yl group). ],

Alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms (eg, ethynyl group, propargyl group, trimethylsilylethynyl group), aryl group (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted, aromatic or non-substituted It is a monovalent group obtained by removing one hydrogen atom from an aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl ,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an n-octyloxy group, a 2-methoxyethoxy group), An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetra A decanoylaminophenoxy group), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as a trimethylsilyloxy group or a tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably having a carbon number of 2 to 30) Substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazo Ru-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms). Substituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group),

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N -Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, Ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as pheno Aryloxycarbonyl group, p- methoxyphenoxy carbonyloxy group, p-n-hexadecyloxycarbonyl phenoxycarbonyl group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino Group (preferably a substituted or unsubstituted amino group having 1 to 30 carbon atoms) Carbonylamino, e.g., carbamoylamino group, N, N-dimethylaminocarbonyl amino group, N, N-diethylamino carbonyl amino group, a morpholinocarbonylamino group),

Alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N -Methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m-n-octyloxyphenoxycarbonylamino group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, , N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, 6 to 30 carbon atoms). Substituted or unsubstituted arylsulfonylamino group, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group),

Mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably substituted or unsubstituted group having 6 to 30 carbon atoms) Substituted arylthio, such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2- Benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3 -Dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl or arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or An unsubstituted alkylsulfinyl group, 6-30 substituted or unsubstituted arylsulfinyl groups such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group)

An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, or a phenylsulfonyl group; , P-methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon number 4 Heterocyclic carbonyl group bonded to carbonyl group with -30 substituted or unsubstituted carbon atoms, for example, acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenyl Carbonyl group, 2-pyridylcarbonyl group, 2-furyl A sulfonyl group), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, p- tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group) Group),

A carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), an aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, , Phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphite Group, diphenylphosphino group, methylphenoxy phosphino group),

A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably carbon A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinylamino group such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as , Trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group) It is.

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  When the ultraviolet absorber represented by any one of the general formulas (1) to (8) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).

  Of the ultraviolet absorbers represented by any of the above general formulas (1) to (8), the ultraviolet absorber itself has a high light fastness, and is represented by any one of the general formulas (1) to (4). In view of the absorption characteristics, those represented by any one of (1) to (3) are preferred, and among them, the compound represented by the general formula (1) or (3) is particularly preferred. On the other hand, when used under basic conditions, a compound represented by any one of the general formulas (4) to (8) is preferable from the viewpoint that coloring due to dissociation does not occur.

The compounds represented by any one of the general formulas (1) to (8) are disclosed in JP-B-48-30492, JP-A-55-36984, JP-A-55-125875, JP-A-36-10466, JP-A-48-596, JP-A-46-3335, 58-214152, 58-221844, 47-10537, 59-19945, 63-53544, 51-56620, 53-128333, 58-181040, JP-A-6-2111813, 7-258228, 8-239368, 8-53427, 10-115898, 10-147777, 10-182621, Special Tables such as Table 5-8501291, U.S. Pat. Nos. 3,754,919, 4,220,711, 2,719,086, 3,698,7 No. 7, No. 3,707,375, No. 5,298,380, No. 5,500,332, No. 5,585,228, No. 5,814,438, British Patent No. 1,198,337 , European Patent Nos. 323408A, 520938A, 521823A, 531258A, 530135A, 5200938A, and the like. Tinuvin 900 (both trade names, manufactured by Ciba Specialty Chemicals Co., Ltd.) is preferable. The compound represented by any one of the general formulas (1) to (8) can be synthesized according to the method described or the method described therein.
The structure of typical UV absorbers and their physical properties and mechanism of action are described in Andreas Valet, “Light Stabilizers for Paint”, published by Vincentz.

<Back layer (heat-resistant slip layer)>
The back surface of the thermal transfer ink sheet travels while being heated in direct contact with a heating device such as a thermal head. Therefore, a back layer (heat resistant slipping layer) is provided in order to prevent thermal fusion between the back surface of the support and a heating device such as a thermal head and to smooth the running.
Cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose butyrate, nitrocellulose, and vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone , Acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymer, polyamide resin, polyvinyl toluene resin, coumarone indene resin, polyester resin, polyurethane resin, silicone modified or fluorine modified A simple substance or a mixture of natural or synthetic resins such as urethane resin and silicone resin can be used.

In order to improve the heat resistance of the back layer, it is also a preferred embodiment to use a crosslinking agent as a crosslinked resin layer.
Furthermore, in order to improve the running property, it is preferable that the back layer contains a solid or liquid release agent or lubricant. Known ones can be used, for example, zinc stearate, stearamide, kaunauba wax, mondan wax, polyethylene wax, paraffin wax and other waxes, higher fatty acid alcohol, organopolysiloxane, anionic interface Activators, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorosurfactants, organic carboxylic acids and their derivatives, fluororesins, silicone resins, phosphate ester compounds, organic or inorganic And the like.

  Such a back layer (heat resistant slipping layer) can be formed using a known coating method. The thickness is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.5 to 3 μm.

2) Thermal transfer image receiving sheet Next, a thermal transfer image receiving sheet (image receiving sheet) will be described.
The heat-sensitive transfer image-receiving sheet used in the present invention has at least one dye-receiving layer (receiving layer) on a support, and at least one heat-insulating layer (porous layer) between the support and the receiving layer. Have In addition, an underlayer such as a white background adjusting layer, a charge adjusting layer, an adhesive layer, or a primer layer may be formed between the receiving layer and the heat insulating layer.
The receiving layer and the heat insulating layer are preferably formed by simultaneous multilayer coating. When the underlayer is included, the receiving layer, the underlayer and the heat insulating layer can be formed by simultaneous multilayer coating.
It is preferable that a curl adjusting layer, a writing layer, and a charge adjusting layer are formed on the back side of the support. Each layer on the back side of the support can be applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.

<Receptive layer>
[Thermoplastic resin]
In the present invention, a thermoplastic resin is preferably used for the receiving layer. Examples of preferred thermoplastic resins include halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, ethylene vinyl acetate copolymer, vinyl chloride vinyl acetate copolymer, polyacrylic ester, polystyrene, polystyrene acrylic, etc. Vinyl resins, acetal resins such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone (Placcel H-5, trade name, manufactured by Daicel Chemical Industries, Ltd.) Polycarbonate resin, cellulose resin and cellulose acetate butyrate described in JP-A-4-296595 and JP-A-2002-264543 (CAB551-0.2, CAB321-0.1, Izu) Trade name, manufactured by Eastman Chemical Company) cellulose resins such as polyolefin resins such as polypropylene, polyamide resins such as urea resins, melamine resins, benzoguanamine resins. These resins can be arbitrarily blended and used within a compatible range. JP-A-57-169370, JP-A-57-207250, JP-A-60-25793, etc. also disclose resins having a receiving layer formed therein.

  Among the above polymers, it is more preferable to contain polycarbonate, polyester, polyurethane, polyvinyl chloride and a copolymer thereof, styrene-acrylonitrile copolymer, polycaprolactone or a mixture thereof, and polycarbonate, polyester, polyvinyl chloride and a copolymer thereof. A combination or a mixture thereof is particularly preferred. Polycarbonate, polyester, and polyvinyl chloride will be described in more detail. The above polymers can be used alone or as a mixture thereof.

(Polyester polymer)
The polyester polymer used for the receiving layer will be described in more detail. Polyester is obtained by polycondensation of a dicarboxylic acid component (including derivatives thereof) and a diol component (including derivatives thereof). The polyester polymer contains an aromatic ring and / or an alicyclic ring. Regarding the technology of alicyclic polyester, the technology described in JP-A-5-238167 is effective in terms of dye uptake ability and image stability.

  The dicarboxylic acid component is selected from adipic acid, azelaic acid, isophthalic acid, trimellitic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, and a mixture of two or more thereof. Preferably, it is selected from isophthalic acid, trimellitic acid, terephthalic acid, or a mixture of two or more thereof. Inclusion of an alicyclic component as the dicarboxylic acid component is more desirable from the viewpoint of improving light resistance. More preferably, 1,4-cyclohexanedicarboxylic acid and isophthalic acid are used. The dicarboxylic acid component is used in a proportion of 50 to 100 mol% of isophthalic acid, 0 to 1 mol% of trimellitic acid, 0 to 50 mol% of terephthalic acid, and 0 to 15 mol% of 1,4-cyclohexanedicarboxylic acid. To do.

  The diol component can be selected from ethylene glycol, polyethylene glycol, tricyclodecane dimethanol, 1,4-butanediol, bisphenol, or a mixture of two or more thereof. Preferably, it is selected from ethylene glycol, polyethylene glycol, and tricyclodecane dimethanol. It is more desirable to include an alicyclic component as a diol component from the viewpoint of improving light resistance. In addition to tricyclodecane dimethanol, alicyclic diol components such as cyclohexane diol, cyclohexane dimethanol, and cyclohexane diethanol can be used. A preferred alicyclic diol component is tricyclodecane dimethanol. The diol component is ethylene glycol 0 to 50 mol /%, polyethylene glycol 0 to 10 mol /%, tricyclodecane dimethanol 0 to 90 mol /%, preferably 30 to 90 mol /%, more preferably 40 to 90 mol /%, 4-butanediol is used at a ratio of 0 to 50 mol /% and bisphenol A 0 to 50 mol /% so that the total amount is 100 mol%.

  In the present invention, at least the above-described dicarboxylic acid component and diol component are used so that the molecular weight (mass average molecular weight (Mw)) is usually about 11,000 or more, preferably about 15000 or more, more preferably about 17000 or more. Polycondensed polyester polymer is used. If the molecular weight is too low, the elasticity of the receiving layer formed will be low and the heat resistance will be insufficient, so it will be difficult to ensure the releasability between the thermal transfer ink sheet and the thermal transfer image receiving sheet. There is a case. The molecular weight is preferably as large as possible from the viewpoint of increasing the elastic modulus, and cannot be dissolved in the coating solution solvent at the time of forming the receiving layer, or the adhesiveness to the base sheet may be adversely affected after the receiving layer is applied and dried. There is no particular limitation as long as no adverse effects occur, but it is preferably about 25,000 or less, and at most about 30000. In addition, what is necessary is just to use a conventionally well-known method as a synthesis method of ester polymer.

  Examples of saturated polyesters include Byron 200, Byron 290, Byron 600, etc. (all trade names, manufactured by Toyobo Co., Ltd.), KA-1038C (trade names, manufactured by Arakawa Chemical Industries, Ltd.), TP220, TP235 (all A trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.) is used.

(Polycarbonate polymer)
The polycarbonate-based polymer used for the receiving layer will be described in more detail. Polycarbonate means polyester having units of carbonic acid and diol, and can be synthesized by a method of reacting diol with phosgene or a method of reacting carbonate ester.

  Diol components include bisphenol A, ethylene glycol, propylene glycol, diethylene glycol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, nonanediol, 4,4'-bicyclo (2,2,2) hept 2-ylidenebisphenol, 4,4 ′-(octahydro-4,7-methano-5H-indene-5-ylidene) bisphenol and 2,2 ′, 6,6′-tetrachlorobisphenol A, and bisphenol A, ethylene glycol, diethylene glycol, butanediol and pentanediol are preferred, bisphenol A, ethylene glycol and butanediol are more preferred, and bisphenol A and ethylene glycol are particularly preferred. The polycarbonate used in the present invention uses at least the above-mentioned one kind of diol component, but a plurality of diols may be mixed and used.

  The bisphenol A-polycarbonate, which is a particularly preferred embodiment of the polycarbonate used in the present invention, will be described in detail. The technique of unmodified polycarbonate, centered on bisphenol A-polycarbonate, is described in US Pat. No. 4,695,286. The polycarbonate used in the present invention has a polycondensation having a molecular weight (mass average molecular weight (Mw)) of usually about 1000 or more, preferably about 3000 or more, more preferably about 5000 or more, particularly preferably about 10,000 or more. Polycarbonates such as Makrolon-5700 (trade name, manufactured by Bayer AG) and LEXAN-141 (trade name, manufactured by General Electric) can be mentioned as examples.

  A technique for producing a modified polycarbonate by mixing bisphenol A and a diol such as ethylene glycol is described in US Pat. No. 4,927,803. The polyether block unit can be formed from a linear aliphatic diol having from 2 to about 10 carbon atoms, but is preferably formed from ethylene glycol. In a preferred embodiment of the present invention, the polyether block units have a number molecular weight of about 4,000 to about 50,000 and the bisphenol A-polycarbonate block units have a number molecular weight of about 15,000 to about 250,000. The overall molecular weight of the block copolymer is preferably from about 30,000 to about 300,000. Specific examples thereof include Makrolon KL3-1013 (trade name, manufactured by Bayer AG).

  It is also preferable to mix these unmodified and modified bisphenol A-polycarbonates, and it is preferable to blend unmodified bisphenol A-polycarbonates and polyether-modified polycarbonates in a mass ratio of 80:20 to 10:90, improving fingerprint resistance. From the viewpoint of mass ratio, a mass ratio of 50:50 to 40:60 is particularly preferable. The blending technology of unmodified and modified bisphenol A-polycarbonate is also described in JP-A-6-227160.

  As a preferred embodiment of the thermoplastic resin used in the receiving layer, a blend system of the above polycarbonate and the above polyester can be mentioned. In this blend system, it is preferable that the compatibility between the polycarbonate and the polyester can be ensured. The polyester preferably exhibits a glass transition temperature (Tg) of about 40 to about 100 ° C, and the polycarbonate exhibits a Tg of about 100 to about 200 ° C. The polyester preferably exhibits a lower Tg than polycarbonate and acts as a polymer plasticizer for the polycarbonate. The Tg of the final polyester / polycarbonate blend is preferably 40 ° C to 100 ° C. Higher Tg polyester and polycarbonate polymers can also be useful by adding plasticizers.

  In a further preferred embodiment, the unmodified bisphenol A-polycarbonate and the polyester polymer are blended in a mass ratio that will bring the final blend Tg to the desired value and minimize cost. The polycarbonate and polyester polymer can be conveniently blended in a mass ratio of about 75:25 to 25:75, but more preferably in a mass ratio of about 60:40 to about 40:60. Japanese Patent Application Laid-Open No. 6-227161 discloses a technique of blending polycarbonate and polyester.

  In the polycarbonate used in the receiving layer, a polymer network structure is formed in the receiving layer by reacting the polycarbonate having an average molecular weight of about 1000 to about 10,000 having at least two hydroxyl groups with a crosslinking agent that reacts with hydroxyl groups. It may be formed. As described in JP-A-6-155933, there is also a technique of a crosslinking agent such as a polyfunctional isocyanate, which can improve the adhesion to a dye donor after transfer. Furthermore, as in the technique disclosed in Japanese Patent Laid-Open No. 8-39942, there is also a technique for constructing a thermal transfer receiving sheet using dibutyltin diacetate in the crosslinking reaction between polycarbonate and isocyanate. It is also possible to improve image stability and fingerprint resistance.

(Vinyl chloride polymer)
A vinyl chloride polymer used for the receiving layer, particularly a copolymer using vinyl chloride, will be described in more detail.
The vinyl chloride copolymer preferably has a vinyl chloride component content of 85 to 97% by mass and a polymerization degree of 200 to 800. The monomer copolymerized with vinyl chloride is not particularly limited, as long as it can be copolymerized with vinyl chloride, and vinyl acetate is particularly preferable. Therefore, vinyl chloride-vinyl acetate copolymer is excellent as the vinyl chloride polymer used in the receiving layer, but vinyl chloride-vinyl acetate copolymer is not necessarily a copolymer of only vinyl chloride component and vinyl acetate component. It may contain a vinyl alcohol component, a maleic acid component, etc. of the range which does not interfere with the objective of this invention not only in a certain case. Other monomer components constituting such a copolymer comprising vinyl chloride and vinyl acetate as main monomers include vinyl alcohol derivatives such as vinyl alcohol and vinyl propionate; acrylic acid and methacrylic acid and their Acrylic acid and methacrylic acid derivatives such as methyl, ethyl, propyl, butyl, 2-ethylhexyl ester; maleic acid derivatives such as maleic acid, diethyl maleate, dibutyl maleate, dioctyl maleate; methyl vinyl ether, butyl vinyl ether, 2-ethylhexyl Vinyl ether derivatives such as vinyl ether; acrylonitrile, methacrylonitrile, styrene and the like. The component ratio of vinyl chloride and vinyl acetate incorporated in the copolymer may be any ratio, but the vinyl chloride component is preferably 50% by mass or more in the copolymer. Moreover, it is preferable that components other than vinyl chloride and vinyl acetate mentioned above are 10 mass% or less.

  Such vinyl chloride-vinyl acetate copolymers include SOLBIN C, SOLBIN CL, SOLBIN CH, SOLBIN CN, SOLBIN C5, SOLBIN M, SOLBIN MF, SOLBIN A, SOLBIN AL, SOLBIN TA5R, SOLBIN TAO, SOLBIN, MOL SOLBIN TA2 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), ESREC A, ESREC C, ESREC M (all trade names, manufactured by Sekisui Chemical Co., Ltd.), Vinylite VAGH, Vinylite VYHH, Vinylite VMCH, VINYLITE VYHD, VINYLITE VYLF, VINYLITE VYNS, VINYLITE VMCC, VINYLITE VMCA, VINYLITE VAGD, VINYLITE VERR, VINYLITE VROH (all trade names and unions) DENKA Vinyl 1000GKT, Denka Vinyl 1000L, Denka Vinyl 1000CK, Denka Vinyl 1000A, Denka Vinyl 1000LK2, Denka Vinyl 1000AS, Denka Vinyl 1000MT2, Denka Vinyl 1000CSK, Denka Vinyl 1000CS, Denka Vinyl 1000 Vinyl GS, Denka Vinyl 1000vinyl LS Any of them may be trade names, manufactured by Denki Kagaku Kogyo Co., Ltd.).

(Polymer latex)
In the present invention, a polymer latex can be preferably used in addition to the above. Hereinafter, the polymer latex will be described.
In the heat-sensitive transfer image-receiving sheet used in the present invention, the polymer latex that can be used in the receiving layer is preferably a polymer in which a hydrophobic polymer containing water-insoluble vinyl chloride as a monomer unit is dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978); Takaaki Sugimura, Akio Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Publications (1993); Soichi Muroi, “Chemistry of Synthetic Latex”, published by High Polymer Publications (1970); 2004) and JP-A-64-538. The average particle size of the dispersed particles is preferably about 1 to 50000 nm, more preferably about 5 to 1000 nm.
The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

  The polymer latex may be a normal uniform structure polymer latex or a so-called core / shell type latex. At this time, it may be preferable to change the glass transition temperature between the core and the shell. The glass transition temperature of the polymer latex used in the present invention is preferably −30 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., further preferably 10 ° C. to 70 ° C., and particularly preferably 15 ° C. to 60 ° C.

  As the polymer latex used in the receiving layer, polyvinyl chlorides and copolymers containing vinyl chloride as monomer units, for example, vinyl chloride vinyl acetate copolymers and vinyl chloride acrylic copolymer polymers can be preferably used. In this case, the ratio of the vinyl chloride monomer is preferably 50% to 95%. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or two or more types of monomers. It may be a polymerized copolymer. In the case of a copolymer, it may be a random copolymer or a block copolymer. The number average molecular weight of these polymers is usually 5,000 to 100,000, preferably 10,000 to 500,000. When the molecular weight is too small, the layer containing the latex may have insufficient mechanical strength, and when it is too large, the film formability may be poor. A crosslinkable polymer latex is also preferably used.

  The polymer latex that can be used in the present invention is commercially available, and the following polymers can be used. Examples include G351 and G576 manufactured by Nippon Zeon Co., Ltd., Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683, 680 manufactured by Nissin Chemical Industry Co., Ltd. 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. (all are trade names).

These polymer latexes may be used alone or in combination of two or more as required.
In the receiving layer, the copolymer latex containing vinyl chloride as a monomer unit is preferably 50% or more in terms of the total solid content in the layer.

  In the present invention, it is preferable to prepare the receptor layer by applying an aqueous coating solution and then drying it. However, “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water. Components other than water in the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxyethylphenyl A water-miscible organic solvent such as ether can be used.

The minimum film-forming temperature (MFT) of the polymer latex is usually −30 ° C. to 90 ° C., preferably about 0 ° C. to 70 ° C. In order to control the minimum film forming temperature, a film forming aid may be added. The film-forming aid is also called a temporary plasticizer and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex. Year). Preferred examples of the film-forming aid include the following compounds, but the film-forming aid that can be used in the present invention is not limited to the following specific examples.
Z-1: benzyl alcohol Z-2: 2,2,4-trimethylpentanediol-1,3-monoisobutyrate Z-3: 2-dimethylaminoethanol Z-4: diethylene glycol

  In the present invention, the above polymer latex may be used (blended) with other polymer latex. Preferable examples of such polymer latex include polylactic acid esters, polyurethanes, polycarbonates, polyesters, polyacetals, and SBRs. Among these, polyesters and polycarbonates can be mentioned.

  Furthermore, the polymer latex used in the present invention may be used in combination with any polymer together with the polymer latex. The polymer that can be used in combination is preferably transparent or translucent and colorless. Natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other media for forming films such as gelatins and polyvinyl alcohol , Hydroxyethylcelluloses, cellulose acetates, cellulose acetate butyrate, polyvinylpyrrolidones, casein, starch, polyacrylic acids, polymethylmethacrylic acids, polyvinylchlorides, polymethacrylic acids, styrene-maleic anhydride copolymers Styrene-acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, Phenoxy resins, polyvinylidene chlorides, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, polyamides such. The binder may be formed from water, an organic solvent, or an emulsion.

  The binder used in the present invention preferably has a glass transition temperature (Tg) in the range of −30 ° C. to 70 ° C., more preferably in the range of −10 ° C. to 50 ° C. in view of processing brittleness and image storage stability. Preferably it is the range of 0 degreeC-40 degreeC. It is also possible to use a blend of two or more polymers as the binder, and in this case, it is preferable that the weighted average Tg in consideration of the composition falls within the above range. Moreover, when phase-separating or having a core-shell structure, the weighted average Tg is preferably within the above range.

This glass transition temperature (Tg) can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

  In the present invention, the polymer used for the binder can be easily obtained by a solution polymerization method, suspension polymerization method, emulsion polymerization method, dispersion polymerization method, anion polymerization method, cationic polymerization, etc. Legal is most preferred. Also preferred is a method of preparing a polymer in a solution and neutralizing or adding an emulsifier and then adding water and forcibly stirring to prepare an aqueous dispersion. In the emulsion polymerization method, for example, water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) is used as a dispersion medium, and the monomer is 5 to 150% by mass with respect to the dispersion medium. An emulsifier and a polymerization initiator are used with respect to the mixture and the total amount of monomers, and the polymerization is usually carried out with stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 24 hours. Various conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the dispersant amount, the reaction temperature, and the monomer addition method are appropriately set in consideration of the type of monomer used. Moreover, it is preferable to use a dispersing agent as needed.

  In the polymer latex used in the present invention, an aqueous solvent can be used as a solvent in the coating solution, but a water-miscible organic solvent may be used in combination. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide. The amount of these organic solvents added is preferably 50% by mass or less, more preferably 30% by mass or less of the solvent.

The polymer latex used in the image forming method of the present invention preferably has a polymer concentration of 10 to 70% by mass, more preferably 20 to 60% by mass, particularly 30 to 55% by mass, based on the latex liquid. Is preferred.
In addition, the polymer latex in the image receiving sheet used in the image forming method of the present invention includes a gel or a dried film formed by drying a part of the solvent after coating.

[Emulsified dispersion]
In the present invention, it is preferable to contain an emulsified dispersion (emulsion) in the receiving layer. This is particularly preferable when a polymer latex is used.
Here, “emulsification” follows the commonly used definition. For example, according to the Dictionary of Chemistry (Kyoritsu Shuppan Co., Ltd.), “emulsification” is defined as “a phenomenon in which another liquid that does not dissolve in one liquid is dispersed as fine particles to produce an emulsion”. The “emulsified dispersion” refers to “liquid droplets that are dispersed in another liquid that does not dissolve them”. In the present invention, a preferable “emulsified dispersion” is an “oil droplet dispersion dispersed in water”. The content of an emulsified dispersion in the image-receiving sheet for use in the image forming method of the present invention is preferably contained 0.03g / m ² ~25.0g / m ² in the image-receiving sheet, 1.0 g / m ² ~ More preferably, 20.0 g / m ^{2 is} contained.

In the present invention, it is preferable that a high boiling point solvent is contained in the oil-soluble component of the emulsified dispersion. Preferred high boiling point solvents include phthalates (dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc.), phosphoric acid or phosphonic esters (triphenyl phosphate, tricresyl phosphate, triphosphate phosphate). 2-ethylhexyl, etc.), fatty acid esters (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoates (2-ethylhexyl benzoate, dodecyl benzoate, etc.), amides (N, N-diethyl, etc.) Dodecanamide, N, N-dimethyloleamide, etc.), alcohol or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-) tert-octylaniline), chlorinated paraffins, hydrocarbons ( Decylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (2- (2,4-di-tert-amylphenoxy) butyric acid, etc. More preferably, the high boiling point solvent is phosphoric acid or phosphonic acid esters (phosphoric acid triphosphate). Phenyl, tricresyl phosphate, tri-2-ethylhexyl phosphate, etc. In addition, as an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethyl) The high boiling point solvent is preferably contained in the emulsion dispersion in an amount of 3.0 to 25% by mass, more preferably 5.0 to 20% by mass.
Further, the emulsified dispersion preferably contains an image fastening agent and an ultraviolet absorber. As these compounds, the general formulas (B), (Ph), (E-1) to (E-3), (TS-I) to (TS-VII) described in JP-A-2004-361936, A compound represented by any of (TS-VIIIA) and (UA) to (UE) is preferable. Further, it may contain a water-insoluble and organic solvent-soluble homopolymer or copolymer (preferably the compounds described in paragraph Nos. 0208 to 0234 of JP-A No. 2004-361936).

[Plasticizer]
In order to improve the sensitivity of the receiving layer, a plasticizer (high boiling point organic solvent) can also be added. Examples of such plasticizers include monomeric plasticizers such as phthalic acid esters, phosphoric acid esters, adipic acid esters, and sebacic acid esters, and polyester-type plasticizers obtained by polymerizing adipic acid, sebacic acid, and propylene glycol. In general, those which can be used as plasticizers for vinyl chloride resins are mentioned. The plasticizers listed above generally have a low molecular weight, but other olefin-based special copolymer resins used as vinyl chloride polymer plasticizers can also be used. Resins used for such applications are commercially available as Elvalloy 741, Elvalloy 742, Elvalloy HP443, Elvalloy HP553, Elvalloy EP4015, Elvalloy EP4043, Elvalloy EP4051 (all trade names, manufactured by Mitsui DuPont Polychemical Co., Ltd.). You can use what you have. Such a plasticizer can be added in an amount of about 100% by mass with respect to the resin, but the amount used is preferably 30% by mass or less in terms of bleeding of the printed matter. In addition, when using polymer latex, it is preferable to use these plasticizers as an emulsified dispersion as mentioned above.

  The receptor layer can be cast by extrusion coating the melt of the polymer resin, without solvent application. This extrusion coating technique is described in Encyclopedia of Polymer Science and Engineering, Volume 3 (John Wiley, New York), 1985, p. 563, 6 Volume, 1986, page 608. Japanese Patent Application Laid-Open No. 7-179075 also discloses a technique relating to a thermal dye transfer material, and this technique can also be suitably used. As the polymer resin, a copolymer obtained by condensing cyclohexane dicarboxylate and a 50/50 mol% mixture (COPOL; registered trademark) of ethylene glycol / bisphenol A-diethanol is particularly preferable.

[Release agent]
If the image-receiving surface of the heat-sensitive transfer image-receiving sheet does not have sufficient peeling performance, the thermal transfer ink sheet and the heat-sensitive transfer image-receiving sheet (image-receiving sheet) are fused by the heat from the thermal head during image formation, and a large peeling sound is generated at the time of peeling. There arises a problem of so-called abnormal transfer that occurs, the dye layer is transferred with the layer, or the receiving layer is peeled off from the substrate. As a method for solving the above problem of peelability, there are known a method of internally adding various release agents into the receiving layer, or a method of separately providing a release layer on the receiving layer. In the present invention, it is preferable to use a release agent in the receiving layer in order to ensure the releasability between the thermal transfer ink sheet and the image receiving sheet during image printing.
Examples of release agents include solid waxes such as polyethylene wax, amide wax, and Teflon powder (Teflon: registered trademark); silicone oil, phosphate ester compounds, fluorine surfactants, silicone surfactants, and others. Release agents known in the art can be used, and silicone compounds such as fluorine compounds represented by fluorine surfactants, silicone surfactants, silicone oils and / or cured products thereof can be used. Preferably used.

  As the silicone oil, straight silicone oil, modified silicone oil or a cured product thereof can be used. Straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of dimethyl silicone oil include KF96-10, KF96-100, KF96-1000, KF96H-10000, KF96H-12500, and KF96H. -100,000 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as dimethyl silicone oil, KF50-100, KF54, KF56 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned.

  The modified silicone oil can be classified into a reactive silicone oil and a non-reactive silicone oil. The reactive silicone oil includes amino modification, epoxy modification, carboxyl modification, hydroxy modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity and heterofunctional modification. As amino-modified silicone oil, KF-393, KF-857, KF-858, X-22-3680, X-22-3801C, KF-8010, X-22-161A, KF-8012 (all trade names, Shin-Etsu Chemical Co., Ltd.), etc., and epoxy-modified silicone oils include KF-100T, KF-101, KF-60-164, KF-103, X-22-343, X-22-3000T ( All of them are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the carboxyl-modified silicone oil include X-22-162C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxy-modified silicone oil include X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176DX, X-22-176D, X-22-176DF (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-164A, X-22-164C, X-24-8201, X-22-174D, X-22-2426 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. .

  The reactive silicone oil can be used after being cured, and can be classified into a reaction curable type, a photo curable type, a catalyst curable type, and the like. Of these, reaction-curable silicone oils are particularly preferable. As the reaction-curable silicone oils, those obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil are preferable. Further, as the catalyst curable type or photo curable type silicone oil, KS-705F-PS, KS-705F-PS-1, KS-770-PL-3 [catalyst curable type silicone oil: all trade names, Shin-Etsu Chemical Co., Ltd. Co., Ltd.], KS-720, KS-774-PL-3 [photocured silicone oil: trade names, manufactured by Shin-Etsu Chemical Co., Ltd.], and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30% by mass of the resin constituting the image receiving layer. The release agent is usually used in an amount of 2 to 4% by mass, preferably about 2 to 3% by mass, based on 100 parts by mass of the polyester resin. If the amount is too small, the releasability cannot be ensured, and if the amount is too large, the protective layer will not be transferred to the image receiving sheet.

  Non-reactive silicone oils include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, fluorine modification and the like. Examples include polyether-modified silicone (KF-6012, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and methylstil-modified silicone silicone oil (24-510, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned. Moreover, the modified silicone represented by either of the following general formulas 1-3 can also be used.

  In general formula 1, R represents a hydrogen atom or a linear or branched alkyl group which may be substituted with an aryl group or a cycloalkyl group. m and n each independently represent an integer of 2000 or less, and a and b each independently represent an integer of 30 or less.

  In General Formula 2, R represents a hydrogen atom or a linear or branched alkyl group which may be substituted with an aryl group or a cycloalkyl group. m represents an integer of 2000 or less, and a and b each independently represent an integer of 30 or less.

In General Formula 3, R represents a hydrogen atom or a linear or branched alkyl group which may be substituted with an aryl group or a cycloalkyl group. m and n each independently represent an integer of 2000 or less, and a and b each independently represent an integer of 30 or less. R ¹ represents a single bond or a divalent linking group, E represents an ethylene group or a substituted ethylene group, and P represents a propylene group or a substituted propylene group.

Silicone oils such as those described above are described in “Silicone Handbook” (published by Nikkan Kogyo Shimbun Co., Ltd.), and are described in JP-A-8-108636 and JP-A-2002-264543 as curing technologies for curable silicone oils. The technique can be preferably used.
Note that abnormal transfer may occur in which the dye binder is taken on the receiving layer in the highlight portion of the monochromatic print. In addition, conventionally, addition polymerization type silicones generally proceed with a curing reaction in the presence of a catalyst, and almost all of the Group 8 transition metal complexes of the iron group and platinum group are effective as the curing catalyst. Although it is known that platinum compounds are generally the most efficient, platinum catalysts that are platinum complexes that are usually soluble in silicone oil are preferably used. As an addition amount necessary for the reaction, about 1 to 100 ppm is sufficient.

  This platinum catalyst has a strong interaction with organic compounds containing multiple bonds, such as organic compounds containing N, P, S, etc., heavy metal ionic compounds such as Sn, Pb, Hg, Bi, As, acetylene groups, etc. When used together with the above compounds (catalyst poisons), the ability to hydrosilylate as a catalyst is lost, and the function as a curing catalyst is lost, so there is a drawback of causing poor curing of the silicone ("Silicone Handbook" Nikkan Kogyo). Newspaper company). Therefore, such a poorly cured addition polymerization type silicone does not exhibit any peeling performance even when used in the receiving layer. It is conceivable to use an isocyanate compound as a curing agent that reacts with active hydrogen, and this isocyanate compound and the organotin compound as a catalyst thereof are catalyst poisons of a platinum catalyst. Therefore, conventionally, the addition polymerization type silicone is not used in combination with an isocyanate compound, and thus is not used in combination with a modified silicone having active hydrogen that exhibits a peeling performance when cured with an isocyanate compound. .

  However, 1) the ratio of the reactive group equivalent of the curing agent that reacts with active hydrogen and the reactive group equivalent of both the thermoplastic resin and the modified silicone having active hydrogen is 1: 1 to 10: 1. 2) Addition polymerization type By setting the platinum catalyst amount with respect to silicone to 100 to 10,000 ppm as platinum atoms of the platinum catalyst, it is possible to prevent curing of the addition polymerization type silicone. When the reactive group equivalent of the curing agent that reacts with the active hydrogen of 1) is 1 or less, the curing amount of the active hydrogen-containing silicone and the active hydrogen of the thermoplastic resin is small, and good release performance is obtained. Absent. On the other hand, when the equivalent ratio is 10 or more, the usable time of the ink of the receiving layer coating liquid is short and cannot be used substantially. Further, when the platinum catalyst amount of 2) is 100 ppm or less, the activity is lost due to the catalyst poison, and when it is 10000 ppm or more, the ink usable time of the receiving layer coating liquid is short and cannot be used.

The coating amount of the receiving layer is preferably 0.5 to 10 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified).

<Release layer>
The cured modified silicone oil may be added to the release layer formed on the receiving layer without being added to the receiving layer. In this case, the receiving layer may be formed using one or more kinds of thermoplastic resins as described above, or a receiving layer to which silicone is added may be used. The release layer contains a curable modified silicone, and the type and usage of the silicone used are the same as those used for the receiving layer. Further, when a catalyst or a retarder is used, it is the same as that added to the receiving layer. The release layer may be formed only from silicone, or may be used as a binder resin by mixing with a compatible resin. The thickness of the release layer is about 0.001 to 1 g / m ^2.

  Fluorosurfactants include Fluorad FC-430 and FC-431 (both trade names, manufactured by 3M).

<Insulation layer>
The image-receiving sheet used in the present invention has at least one heat insulating layer containing hollow polymer particles and a hydrophilic polymer between the receiving layer and the support.
The heat insulating layer serves to protect the support from heat during heat transfer using a thermal head or the like. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the substrate. The heat insulating layer may be one layer or two or more layers. The heat insulating layer is provided on the support side from the receptor layer.

In the image receiving sheet used in the present invention, the heat insulating layer contains a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle. For example, [1] a dispersion medium such as water enters a partition formed by polystyrene, acrylic resin, styrene-acrylic resin or the like. After coating and drying, non-foamed hollow particles in which the dispersion medium in the particles evaporates outside the particles and the inside of the particles becomes hollow, [2] low boiling point liquids such as butane and pentane, polyvinylidene chloride, polyacrylonitrile Foam that is covered with a resin made of polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof, and the inside of which is hollowed by the expansion of the low-boiling liquid inside the particles by heating after coating. Type microballoons, and [3] microballoons obtained by heating and foaming the above [2] in advance to form a hollow polymer.

The particle size of these hollow polymers is preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, still more preferably 0.1 to 1 μm, and particularly preferably 0.2 to 0.8 μm. If the size is too small, the hollowness tends to decrease and the desired heat insulating property cannot be obtained.If the size is too large, the particle diameter of the hollow polymer is too large for the film thickness of the heat insulating layer to obtain a smooth surface. This is because it becomes difficult to cause coating failure due to coarse particles.
The hollow ratio of the hollow polymer is preferably about 20 to 70%, more preferably 20 to 50%. This is because when the hollow ratio is less than 20%, sufficient heat insulation cannot be obtained, and when the hollow ratio is excessively high, the ratio of incomplete hollow particles increases within a preferable particle size range, and sufficient film strength is obtained. This is because it cannot be obtained.
The hollow ratio of the hollow polymer in the present invention is a value P calculated by the following formula (a) in a transmission image taken from a transmission micrograph of the hollow particles.

  In the above formula (a), Rai represents the equivalent circle diameter of the inner contour (indicating the hollow portion contour) of the two contours constituting the image of the specific particle i, and Rbi represents the image of the specific particle i. Of the two contours to be constructed, the equivalent circular diameter of the outer contour (indicating the particle outer shape) is represented, n represents the number of measured particles, and n ≧ 300.

  The glass transition temperature (Tg) of the hollow polymer is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher. Two or more types of hollow polymers can be mixed and used as necessary.

  Such hollow polymers are commercially available, and specific examples of the above [1] include Law and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nippon MH5055 (both are trade names). Specific examples of [2] include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of [3] include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSELL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. Among these, the hollow polymer of the series [1] can be used more preferably.

  The heat insulating layer containing the hollow polymer preferably contains a water-dispersed resin or a water-soluble resin as a binder resin as a binder resin. Examples of the binder resin used in the present invention include acrylic resins, styrene-acrylic copolymers, polystyrene resins, polyvinyl alcohol resins, vinyl acetate resins, ethylene-vinyl acetate copolymers, vinyl chloride vinyl acetate copolymers, and styrene. Known resins such as butadiene copolymers, polyvinylidene chloride resins, cellulose derivatives, casein, starch, and gelatin can be used. In the present invention, it is particularly preferable to use gelatin. These resins can be used alone or in combination.

  The solid content of the hollow polymer in the heat insulating layer is preferably between 5 and 2000 parts by mass, and preferably between 5 and 1000 parts by mass when the solid content of the binder resin is 100 parts by mass. More preferably, it is more preferably between 5 and 400 parts by mass. Moreover, 1-70 mass% is preferable, and, as for the mass ratio which occupies with respect to the coating liquid of the solid content of a hollow polymer, 10-40 mass% is more preferable. If the ratio of the hollow polymer is too small, sufficient heat insulation cannot be obtained, and if the ratio of the hollow polymer is too large, the binding force between the hollow polymers is lowered, sufficient film strength cannot be obtained, and scratch resistance is obtained. Getting worse.

The image-receiving sheet used in the present invention does not contain a resin having no resistance to organic solvents in addition to the hollow polymer in the heat insulating layer. If the heat insulating layer contains a resin that is not resistant to organic solvents (pigment dyeing resin), the image bleeding after the image transfer increases, which is not preferable. This is because the dye-stainable resin and the hollow polymer exist in the heat insulating layer, so that the dye dyed on the receiving layer after the transfer moves over time through the adjacent heat-insulating layer. it is conceivable that.
Here, “not resistant to organic solvent” means that the solubility in an organic solvent (methyl ethyl ketone, ethyl acetate, benzene, toluene, xylene, etc.) is 1% by mass or less, preferably 0.5% by mass or less. Say. For example, the polymer latex is included in “resin not resistant to organic solvent”.

  The thickness of the heat insulating layer containing the hollow polymer is preferably 5 to 50 μm, and more preferably 5 to 40 μm.

The porosity of the heat insulating layer calculated from the thickness of the heat insulating layer containing the hollow polymer and the solid coating amount of the heat insulating layer containing the hollow polymer is preferably 10 to 70%, and more preferably 15 to 60%. When the porosity of the heat insulating layer is less than 10%, sufficient heat insulating properties cannot be obtained, and when it is 70% or more, the binding force between the hollow polymers is lowered, and sufficient film strength cannot be obtained, and the scratch resistance is deteriorated.
In the present invention, the porosity of the heat insulating layer is a value V calculated by the following equation (b).

  In the above formula (b), L represents the film thickness of the heat insulating layer, gi represents the solid coating amount of the specific material i constituting the heat insulating layer, and di represents the specific gravity of the specific material i. Here, when di represents the specific gravity of the hollow polymer, di represents the specific gravity of the wall material of the hollow polymer.

<Underlayer>
An undercoat layer may be formed between the receiving layer and the heat insulating layer. For example, a white background adjusting layer, a charge adjusting layer, an adhesive layer, and a primer layer are formed. About these layers, it can be set as the structure similar to what was described, for example in patent 3585599, patent 2925244, etc.

(Curl adjustment layer)
If the support is exposed as it is, the heat-sensitive transfer image-receiving sheet may be curled due to the humidity and temperature in the environment. Therefore, it is preferable to form a curl adjusting layer on the back side of the support. The curl adjusting layer not only prevents the image receiving sheet from curling but also serves as a waterproof. For the curl adjusting layer, polyethylene laminate, polypropylene laminate, or the like is used. Specifically, it can be formed in the same manner as described in, for example, JP-A-61-110135 and JP-A-6-202295.

(Writing layer / Charge adjustment layer)
An inorganic oxide colloid, an ionic polymer, or the like can be used for the writing layer and the charge adjusting layer. As the antistatic agent, for example, a cationic antistatic agent such as a quaternary ammonium salt or a polyamine derivative, an anionic antistatic agent such as an alkyl phosphate, or a nonionic antistatic agent such as a fatty acid ester can be used. . Specifically, it can be formed in the same manner as that described in, for example, Japanese Patent No. 3585585.

<Support>
In the present invention, a water-resistant support is used as the support. By using a water-resistant support, it is possible to prevent moisture from being absorbed into the support, and to prevent a change in performance of the receiving layer over time. As the water-resistant support, for example, coated paper or laminated paper can be used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex, or polymer material on one side or both sides of a sheet such as a base paper, and the coating amount varies depending on the application. Examples of such coated paper include art paper, cast coated paper, Yankee paper, and the like.

  As the resin applied to the surface of the base paper or the like, it is appropriate to use a thermoplastic resin. Examples of such a thermoplastic resin include the following thermoplastic resins (a) to (h).

(A) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
(B) A thermoplastic resin having an ester bond. For example, dicarboxylic acid components (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.) and alcohol components (these alcohol components may be substituted with hydroxyl groups, etc.) Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate and other polyacrylate resin or polymethacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene -Methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, etc. are mentioned.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. it can.
Commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd. Polyester TP-220, R manufactured by Nippon Synthetic Chemical Co., Ltd. -188; various types of thermoplastic resins of the Hiros series manufactured by Seiko Chemical Industry Co., Ltd. (all trade names).

(C) Polyurethane resin etc. are mentioned.
(D) Polyamide resin, urea resin, etc. are mentioned.
(E) Polysulfone resin and the like.
(F) Polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
(G) Cellulose resins, such as polyol resin, ethyl cellulose resin, cellulose acetate resin, etc., such as polyvinyl butyral.
(H) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  Further, the thermoplastic resin may contain pigments or dyes such as brighteners, conductive agents, fillers, titanium oxide, ultramarine blue, and carbon black as required.

-Laminated paper-
The laminated paper is a paper obtained by laminating various resins, rubber or polymer sheets or films on a sheet such as a base paper. Examples of the laminate material include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. These resins may be used alone or in combination of two or more.

  In general, the polyolefin is often formed using low density polyethylene, but in order to improve the heat resistance of the support, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, high density polyethylene and low density polyethylene, It is preferable to use a blend of In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of cost, suitability for lamination, and the like.

The blend of the high density polyethylene and the low density polyethylene is used, for example, in a blend ratio (mass ratio) of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When forming a thermoplastic resin layer on both surfaces of the support, the back surface of the support is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. The molecular weight of polyethylene is not particularly limited, but the melt index is 1.0 to 40 g / 10 min for both high-density polyethylene and low-density polyethylene and has extrudability. preferable.
In addition, you may perform the process which gives white reflectivity to these sheets or films. Examples of such a treatment method include a method of blending a pigment such as titanium oxide in these sheets or films.

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose, and the support for a photographic image receiving sheet for electrophotography is close to a support for color silver halide photography. Those are preferred.

Hereinafter, a method for producing a thermal transfer image receiving sheet used in the image forming method of the present invention will be described.
The heat-sensitive transfer image-receiving sheet used in the image forming method of the present invention can be formed by simultaneously applying at least one receptor layer, intermediate layer and heat insulating layer on a support.
When producing a multi-layer image receiving sheet comprising a plurality of layers having different functions (such as a bubble layer, a heat insulating layer, an intermediate layer, and a receiving layer) on a support, JP-A Nos. 2004-106283 and 2004-181888 are disclosed. In addition, it is known that each layer is sequentially coated as disclosed in each publication such as JP-A 2004-345267, or the layers are previously applied on a support and bonded together. On the other hand, it is known in the photographic industry that productivity is greatly improved, for example, by applying a plurality of layers simultaneously. For example, JP-A Nos. 2,761,791, 2,681,234, 3,508,947, 4,457,256, 3,993,019, Kaisho 63-54975, JP-A-61-278848, 55-86557, 52-31727, 55-142565, 50-43140, 63-80872, 54-54020 JP-A-5-104061, JP-A-5-127305, JP-B-49-7050, or specification, Edgar B. Gutoff et al., "Coating and Drying Defects: Troubleshooting Operating Problems", John Wiley & Sons, 1995. , 101-103, etc., so-called slide coating (slide coating method) and curtain coating (curtain coating method) are known.
In the present invention, the simultaneous multi-layer coating is used for manufacturing a multi-layer image-receiving sheet, whereby productivity can be greatly improved and image defects can be greatly reduced.

In the present invention, the plurality of layers are composed mainly of a resin. The coating solution for forming each layer is preferably water-dispersed latex. The solid content mass of the latex resin in the coating solution of each layer is preferably in the range of 5 to 80%, particularly preferably in the range of 20 to 60%. The average particle size of the resin contained in the water-dispersed latex is 5 μm or less and particularly preferably 1 μm or less. The water-dispersed latex may contain a known additive such as a surfactant, a dispersant, and a binder resin as necessary.
In the present invention, it is preferable that a laminate of a plurality of layers is formed on a support by the method described in US Pat. No. 2,761,791, and then quickly solidified. As an example, in the case of a multilayer structure solidified by a resin, it is preferable to quickly raise the temperature after forming a plurality of layers on the support. When a binder that gels at a low temperature such as gelatin is included, it may be preferable to quickly lower the temperature after forming a plurality of layers on the support.
The coating amount of a coating solution per one layer constituting the multilayer in the present invention in the range of 1g / m ² ~500g / m ² is preferred. The number of layers in the multilayer configuration can be arbitrarily selected as 2 or more. The receiving layer is preferably provided as the layer furthest away from the support.

3) Image formation In the image forming method of the present invention, the thermal transfer image-receiving sheet is superposed so that the receiving layer of the thermal transfer image-receiving sheet and the thermal transfer layer of the thermal transfer ink sheet are in contact with each other, and thermal energy is applied according to the image signal from the thermal head. Thus, an image is formed.
When the ink sheet has a protective layer capable of thermal transfer, the protective layer can be transferred onto the image formed on the receiving layer of the image receiving sheet by applying thermal energy from the thermal head.

  Specific image formation can be performed in the same manner as described in, for example, JP-A-2005-88545. In the present invention, the printing time is preferably less than 15 seconds, more preferably 3 to 12 seconds, and even more preferably 3 to 7 seconds from the viewpoint of shortening the time until the printed matter is provided to the consumer.

  In order to satisfy the printing time, the line speed during printing is preferably 0.73 msec / line or less, and more preferably 0.65 msec / line. Further, from the viewpoint of improving transfer efficiency under high speed conditions, the maximum temperature reached by the thermal head during printing is preferably 180 ° C. or higher and 450 ° C. or lower, more preferably 200 ° C. or higher and 450 ° C. or lower. Furthermore, 350 degreeC or more and 450 degrees C or less are preferable.

The present invention can be used in printers, copiers and the like using a thermal transfer recording system. As the means for applying thermal energy at the time of thermal transfer, any conventionally known means for applying can be used. For example, recording is performed by a recording device such as a thermal printer (for example, product name, video printer VY-100, manufactured by Hitachi, Ltd.). By controlling the time, the intended purpose can be sufficiently achieved by applying thermal energy of about 5 to 100 mJ / mm ² . The thermal transfer image-receiving sheet used in the image forming method of the present invention is a sheet- or roll-shaped thermal transfer image-receiving sheet that can be thermally transferred and recorded by appropriately selecting a support. It can also be applied to various uses such as.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In Examples, “part” or “%” is based on mass unless otherwise specified.

[Preparation of thermal transfer ink sheet 101]
(Preparation of thermal transfer ink sheet coating liquid and protective layer coating liquid)
The following coating solutions were prepared for preparing a thermal transfer ink sheet.
<Preparation of coating solution PY-1 for yellow thermal transfer layer>
Yellow dye Y1-6 4.1 parts Yellow dye Y3-7 4.1 parts Polyvinyl acetoacetal resin 8.0 parts (Eslex KS-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Polyvinyl butyral resin 0.2 part (Denkabutyral # 6000-C, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Compound P-1 0.8 part Matting agent 0.15 part (Flosen UF, trade name, manufactured by Sumitomo Seika Co., Ltd.)
84 parts of methyl ethyl ketone / toluene (mass ratio 2/1)

<Preparation of Magenta Thermal Transfer Layer Coating Liquid PM-1>
Magenta Dye M1-2 0.1 part Magenta Dye M2-1 0.7 part Magenta Dye M2-3 6.7 part Cyan Dye C2-2 0.4 part Polyvinylacetoacetal resin 8.0 parts (Eslex KS-1 , Trade name, manufactured by Sekisui Chemical Co., Ltd.)
Polyvinyl butyral resin 0.2 part (Denkabutyral # 6000-C, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Compound P-1 0.8 part Matting agent 0.15 part (Flosen UF, trade name, manufactured by Sumitomo Seika Co., Ltd.)
84 parts of methyl ethyl ketone / toluene (mass ratio 2/1)

<Preparation of Cyan Thermal Transfer Layer Coating Liquid PC-1>
Cyan dye C1-3 1.7 parts Cyan dye C2-2 6.6 parts Polyvinyl acetal resin 8.0 parts (Eslex KS-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Polyvinyl butyral resin 0.2 part (Denkabutyral # 6000-C, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Compound P-1 0.8 part Matting agent 0.15 part (Flosen UF, trade name, manufactured by Sumitomo Seika Co., Ltd.)
84 parts of methyl ethyl ketone / toluene (mass ratio 2/1)

<Preparation of release layer coating liquid PU1 for protective layer capable of thermal transfer>
Modified cellulose resin 5 parts (L-30, trade name, manufactured by Daicel Chemical Industries, Ltd.)
95 parts of methyl ethyl ketone

<Preparation of protective layer release layer coating solution PO1 capable of thermal transfer>
Acrylic resin solution (solid content 40%) 90 parts (UNO-1, trade name, manufactured by Gifu Ceramic Co., Ltd.)
Methanol / isopropanol (mass ratio 1/1) 10 parts

<Preparation of adhesive layer coating liquid A1 for protective layer capable of thermal transfer>
Acrylic resin 25 parts (Diananal BR-77, trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
The following ultraviolet absorbent UV-1 1 part The following ultraviolet absorbent UV-2 2 parts The following ultraviolet absorbent UV-3 1 part The following ultraviolet absorbent UV-4 1 part PMMA fine particles 0.4 part Methyl ethyl ketone / toluene (mass ratio 2 / 1) 70 parts

(Preparation of coating solution for back layer)
The following coating solutions were prepared for the preparation of the heat resistant back layer of the thermal transfer ink sheet.
<Preparation of Back Layer Coating Liquid BC1>
Acrylic polyol resin 26.0 parts (Acridic A-801, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
Zinc stearate 0.43 parts (SZ-2000, trade name, manufactured by Sakai Chemical Industry Co., Ltd.) 1.27 parts Phosphate ester (Pricesurf A217, trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Isocyanate (50% solution) 8.0 parts (Bernock D-800, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl ethyl ketone / toluene (mass ratio 2/1) 64 parts

(Production of sheet by application of the coating solution)
Dry on the surface of the polyester film (diafoil K200E-6F, trade name, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 6.0 μm that has been subjected to easy adhesion treatment on one side as the support. The back layer coating solution BC1 was applied so that the subsequent solid content application amount was 1 g / m ² . After drying, it was cured by heat treatment at 60 ° C.
A thermal transfer ink sheet 101 was prepared by applying the coating liquid to the easy-adhesion layer application side of the polyester film prepared in this manner and applying the yellow, magenta, and cyan thermal transfer layers and the protective layer in the surface order. . In the case of forming a protective layer, the protective layer release layer coating solution PU1 is applied and dried, and then the protective layer release layer coating solution PO1 is applied thereon and dried. Furthermore, the protective layer adhesive layer coating solution A1 was applied thereon.
The coating amount at this time was adjusted such that the solid content coating amount was the following coating amount.

Yellow thermal transfer layer 0.8g / m ²
Magenta thermal transfer layer 0.8g / m ²
Cyan thermal transfer layer 0.8g / m ²
Protective layer release layer 0.3 g / m ²
Protective layer release layer 0.5 g / m ²
Protective layer adhesive layer 2.2 g / m ²

[Preparation of thermal transfer ink sheet 102]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the compound P-1 added to each dye layer was replaced with the compound P-6.
Compound P-6 0.8 part

[Preparation of thermal transfer ink sheet 103]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the polyvinyl acetoacetal resin and polyvinyl butyral resin added to each dye layer were changed to the following compounds.
Cellulose acetate butyrate 8.2 parts

[Preparation of thermal transfer ink sheet 104]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the polyvinyl acetoacetal resin and polyvinyl butyral resin added to each dye layer were changed to the following compound H-1.
Compound H-1 8.2 parts

  In the formula, l, m and n are respectively 66 for l, 8 for m and 26 for n.

[Preparation of thermal transfer ink sheet 105]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the compound P-1 added to each dye layer was changed to the following compound.
Comparative Compound 1 0.04 part (X-22-3000T, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Comparative Compound 2 0.02 part (TSF4701, trade name, manufactured by Momentive Performance Materials Japan GK)

[Preparation of thermal transfer ink sheet 106]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the compound P-1 added to each dye layer was changed to the following compound.
Comparative compound 1 0.10 parts (X-22-3000T, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Comparative compound 2 0.05 parts (TSF4701, trade name, manufactured by Momentive Performance Materials Japan GK)

[Preparation of thermal transfer ink sheet 107]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the compound P-1 added to each dye layer was changed to the following comparative compound.
Comparative compound 3 0.15 parts (Florard FC-430, trade name, manufactured by Sumitomo 3M Limited)

[Preparation of thermal transfer ink sheet 108]
It was produced in the same manner as the thermal transfer ink sheet 101 except that the compound P-1 added to each dye layer was not used.

[Preparation of thermal transfer image-receiving sheet 201]
The surface of the paper support laminated on both sides with polyethylene was subjected to corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate. On this, an undercoat layer, a heat insulating layer, a receiving layer lower layer, and a receiving layer upper layer having the following composition are laminated in this order from the support side in this order, and the 9th described in US Pat. No. 2,761,791 Multilayer coating was performed by the method illustrated in the figure. Each coating amount of the dry subbing layer: 6.7g / m ^2, the heat insulating layer: 8.6g / m ^2, Lower receptor layer: 2.6g / m ^2, Upper receptor layer: 2.7 g / m ² The coating was performed so that
Receptor upper layer Vinyl chloride latex (as solid content) 22.2 parts (Viniblanc 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Vinyl chloride latex (as solids) 2.5 parts (Viniblanc 276, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Gelatin 0.5 part Ester wax EW-1 2.0 part Surfactant F-1 0.04 part Receiving layer lower layer Vinyl chloride latex (as solids) 24.4 parts (Viniblanc 690, trade name, Nissin Chemical Industry Co., Ltd.)
Gelatin 1.4 parts Surfactant F-1 0.04 parts Heat insulation layer Hollow polymer particle latex (as solids) 579 parts (MH5055, trade name, manufactured by Nippon Zeon Co., Ltd.)
Gelatin 279 parts Undercoat layer Polyvinyl alcohol 16.8 parts (Poval PVA205, trade name, manufactured by Kuraray Co., Ltd.)
150 parts of styrene butadiene rubber latex (as solid content) (SN-307, trade name, manufactured by Nippon A & L Co., Ltd.)
The following surfactant F-1 0.1 part

[Preparation of thermal transfer image-receiving sheet 202]
Synthetic paper (YUPO FPG200, thickness 200 μm, trade name, manufactured by YUPO Corporation) was used as the support, and the heat insulating layer of the thermal transfer image-receiving sheet 201 and the following receiving layer were coated on the one surface in this order by a bar coater. . The coating amount at the time of each of the dry heat-insulating layer: 8.6 g / m ^2, to perform coating so that the receptive layer 4.0 g / m ^2, drying each layer 110 ° C., was carried out for 30 seconds.
Receiving layer 100 parts by mass of vinyl chloride-vinyl acetate resin (manufactured by Nissin Chemical Industry Co., Ltd., trade name, Solvein A)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
Epoxy-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3000E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

[Image formation]
The produced thermal transfer ink sheet and image receiving sheet were processed so that they could be loaded into a sublimation thermal transfer printer ASK2000 (trade name) manufactured by FUJIFILM Corporation, and output was performed in a high-speed print mode. At this time, the line speed was 0.73 ms / line, and the maximum temperature reached by TPH was 400 ° C.

[Evaluation test]
(1) Blocking Print 30 sheets of digital image information that will be black solid ((R, G, B) = (0,0,0)) of KG size, and visually check whether blocking occurs due to transfer failure. did. When one of the 30 sheets occurred, it was determined to “occur”.
(2) Ribbon wrinkles (Rs)
Next, ribbon wrinkles were evaluated. In order to print 30 sheets of digital image information and quantify the ribbon wrinkles that occurred on the 30th print, a network scanner ES-2200 (trade name) manufactured by Seiko Epson Corporation was used, 24-bit color, 100 dpi conditions. The print image was taken in and converted into a bmp format data file. At the time of image capture, image analysis was performed using the 98% portion of the center of the screen in order to remove noise information on the screen edge. Ribbon wrinkle image analysis extracts G information having the strongest visibility from this data file, and the ratio of pixels that do not reproduce black indicating 25 or more information to the total number of pixels is the ribbon wrinkle occurrence rate Rs. Defined. If ribbon wrinkles are small, Rs is small, and if it is large, Rs is large. Note that ribbon wrinkle evaluation was not possible for samples in which blocking occurred. The results are shown in Table 2.

As is clear from the results in Table 2, blocking occurred in samples 7 to 10 (comparative examples) using ink sheets 105 to 108 that did not contain the compound represented by the general formula (I) in the thermal transfer layer. Or, ribbon wrinkle occurrence rate Rs was large, and many ribbon wrinkles were generated.
On the other hand, Samples 1 to 6 using the ink sheets 101 to 104 of the present invention containing the compound represented by the general formula (I) in the thermal transfer layer do not generate ribbon wrinkles and block. It was found that high-quality prints can be obtained.

It is a top view which shows one preferable embodiment of the thermal transfer ink sheet of this invention. It is a top view of the thermal transfer ink sheet which formed the ink layer (dye layer) of this invention on the separate support body. It is sectional drawing which shows one preferable embodiment of the thermal transfer ink sheet of this invention.

Explanation of symbols

1 thermal transfer ink sheet 2 substrate film 3 ink layer (dye layer)
4 Transferable protective layer laminate 4a Release layer 4b Protective layer 4c Adhesive layer 5 Back layer Y Yellow dye layer M Magenta dye layer C Cyan dye layer BK Black layer

Claims (8)

A thermal transfer ink sheet having at least a thermal transfer layer containing a thermally transferable dye and a resin on one side of a base film, and having a heat-resistant slipping layer formed on the other side, wherein the thermal transfer layer includes A thermal transfer ink sheet comprising a compound represented by the following general formula (I):

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, provided that the sum of the number of carbon atoms of R ¹ and R ² is 8 to 24. L ¹ is a single bond or Represents a divalent linking group, and M ¹ represents a cation.)   The thermal transfer ink sheet according to claim 1, wherein the thermal transfer layer is coated with a solvent. The thermal transfer ink sheet according to claim 1 or 2, wherein the resin is a resin represented by the following general formula (II).

(In the formula, R represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. L, m and n each represent a ratio of each repeating unit, and the total of l, m and n is 100. 1 represents 10 to 100, m represents 0 to 50, and n represents 0 to 50.)   The thermal transfer ink sheet according to any one of claims 1 to 3, wherein at least three kinds of thermal transfer layers comprising yellow, magenta, and cyan are formed in a surface sequential manner on a single support.   The thermal transfer ink sheet according to any one of claims 1 to 4, further comprising a protective layer capable of thermal transfer.   The thermal transfer ink sheet according to any one of claims 1 to 5, and at least one dye-receiving layer on a support, and hollow polymer particles between the receiving layer and the support. A thermal transfer image receiving sheet having at least one heat insulating layer containing a hydrophilic polymer is overlaid so that the thermal transfer layer of the thermal transfer ink sheet and the receiving layer of the thermal transfer image receiving sheet are in contact with each other. An image forming method comprising forming an image by applying thermal energy according to the method.   7. The image forming method according to claim 6, wherein in the heat-sensitive transfer image-receiving sheet, at least one of the hydrophilic polymers contained in the heat insulating layer is gelatin.   The thermal transfer layer of the thermal transfer ink sheet and the receiving layer of the thermal transfer image receiving sheet are overlapped so that they are in contact with each other, and after forming an image by applying thermal energy according to the image signal from the thermal head, the same thermal head is used. The image forming method according to claim 6, wherein a protective layer is formed on the image formed by thermal transfer.

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