JP2009202541A - Thermosensitive transfer ink sheet, ink cartridge, thermosensitive transfer recording method and composition for dye layer of thermosensitive transfer ink sheet - Google Patents

Abstract

The present invention provides a thermal transfer ink sheet, an ink cartridge, a thermal transfer recording method, and a composition for a dye layer of a thermal transfer ink sheet that achieve both transferability during high-speed transfer and dye storage stability.
A heat transfer dye is contained in a resin binder on a support, and the resin binder of the dye layer includes an α-olefin residue unit and an N-phenyl-substituted maleimide residue unit. And a copolymer having a molar ratio of 49:51 to 35:65.
[Selection figure] None

Description

  The present invention relates to a sublimation type thermal transfer sheet, in particular, a dye layer on a support, and stable release from the thermal transfer image receiving sheet without being affected by the support material of the thermal transfer image receiving sheet. Sublimation-type thermal transfer ink sheet capable of maintaining transfer image formation with good image quality, and composition for dye layer of thermal transfer ink sheet excellent in storage stability of dye-layer ink for sublimation transfer before coating And an ink cartridge and a thermal transfer recording method.

  Conventionally, various thermal transfer recording methods are known. 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. In addition, compared to silver halide photography, it has advantages such as being dry, being able to visualize directly from digital data, being easy to duplicate, and being able to build a system for image formation at a relatively low cost. ing.

In this dye diffusion transfer recording system, a thermal transfer ink sheet (hereinafter also simply referred to as an ink sheet) containing a dye (hereinafter also referred to as a pigment) and a thermal transfer image receiving sheet (hereinafter also simply referred to as an image receiving sheet) are used. Then, 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 In addition, by superimposing and recording three colors of yellow or four colors obtained by adding black to this, a color image having a continuous change in color shading can be transferred and recorded.
Each color dye layer (also referred to as an ink layer) may be formed on separate supports, or may be repeatedly formed in the surface order on the same support. Further, in addition to these dye layers, a protective layer may be formed on the same support so as to cover and protect the image by being thermally transferred onto the image after printing.
The dye layer is provided in any manner depending on the purpose. For example, in addition to general yellow, magenta, cyan and black, a dye layer having an arbitrary hue can be provided.

  As performance required in such image formation, for example, it has desirable spectral characteristics for color reproduction, it is easy to transfer, it is robust to light and heat, it is robust to various chemicals, a material Are easy to synthesize, and a heat-sensitive transfer sheet and a heat-sensitive transfer image-receiving sheet are easy to produce.

  Conventionally, a polyester resin has been used as a resin binder that plays a role of retaining a dye in a thermal transfer ink sheet. In recent years, a polyvinyl acetal resin has been found and used as a polymer material for forming a high-density color image (see Patent Documents 1 and 2). However, in recent years, the printing speed has been remarkably increased, and it has become difficult for these resins to cope with the higher transfer speed and to achieve both the storage stability of the dye.

Japanese Patent No. 3263138 JP-A-7-32742

  It is an object of the present invention to provide a thermal transfer ink sheet, an ink cartridge, a thermal transfer recording method, and a composition for a dye layer of a thermal transfer ink sheet that achieve both transferability during high-speed transfer and dye storage stability.

As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following configuration. That is, the said subject was achieved by the following means.
(1) It has a dye layer in which a heat transferable dye is contained in a resin binder on a support, and the resin binder of the dye layer is an α-olefin residue unit represented by the following formula (i) And a N-phenyl-substituted maleimide residue unit represented by the following formula (ii) in a molar ratio of 49:51 to 35:65 (a). Sheet.

(Here, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently Represents a hydrogen atom, a halogen atom, a carboxyl group or a salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, a cyano group, a nitro group, or a linear or branched alkyl group having 1 to 8 carbon atoms.)
(2) The resin binder of the dye layer further contains an acrylonitrile-styrene copolymer (b) having an acrylonitrile residue unit and a styrene residue unit in a mass ratio of 36:64 to 50:50. The thermal transfer ink sheet according to (1).
(3) The copolymer (a) and the copolymer (b) each have a mass average molecular weight of 5 × 10 ^{3 to} 5 × 10 ⁶ in terms of standard polystyrene (1) or (2) The heat-sensitive transfer ink sheet as described in 1).
(4) The resin binder of the dye layer is composed of 20 to 85% by mass of the copolymer (a) and 80 to 15% by mass of the acrylonitrile-styrene copolymer (b). The thermal transfer ink sheet according to any one of (3).
(5) The copolymer (a) is an N-phenylmaleimide-isobutene copolymer and / or an N- (2-methylphenyl) maleimide-isobutene copolymer (1) to (4) The thermal transfer ink sheet according to any one of 1).
(6) An ink cartridge comprising the thermal transfer ink sheet according to any one of (1) to (5).
(7) Forming an image using the thermal transfer ink sheet according to any one of (1) to (5) on a thermal transfer image-receiving sheet having an ink-receiving layer containing a polymer latex on a support. Thermal transfer recording system characterized by
(8) A coating composition for a dye layer of a thermal transfer ink sheet, comprising a binder containing the copolymer according to any one of (1) to (5) and a heat transferable dye. .

  According to the present invention, it is possible to provide a thermal transfer ink sheet, an ink cartridge, a thermal transfer recording method, and a composition for a dye layer of a thermal transfer ink sheet that achieve both transferability during high-speed transfer and dye storage stability.

  The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present invention, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Thermal transfer ink sheet>
The thermal transfer ink sheet of the present invention will be described.
The heat-sensitive transfer ink sheet of the present invention has at least a dye layer in which a heat transferable dye is contained in a resin binder on a support. Furthermore, it is preferable to have an easy adhesion layer, a transferable protective layer laminate and a back layer as other functional layers. Moreover, you may have a dye barrier layer. In addition, although the transferable protective layer laminated body here refers to the laminated body which consists of a protective layer, a mold release layer, and an adhesive layer generally, the multiple or 1 layer which combines these functions may be sufficient.

[Dye layer]
(Resin binder)
The resin binder of the dye layer of the present invention preferably contains at least a copolymer (a) and further contains an acrylonitrile-styrene copolymer (b). More preferably, the copolymer (a) is 20 to 85% by mass and the acrylonitrile-styrene copolymer (b) is 80 to 15% by mass, and the copolymer (a) from the viewpoint of compatibility between dye preservability and transferability. It is particularly preferable that the composition consists of 30 to 60% by mass and acrylonitrile-styrene copolymer (b) 70 to 40% by mass. Here, when copolymer (a) is 20 mass% or more, since the heat resistance of the resin composition and film which are obtained improves, it is preferable. On the other hand, when the copolymer (a) is 85% by weight or less, transferability is improved, which is preferable.

  The copolymer used in the present invention may be used in combination with any polymer. The polymer that can be used in combination is preferably transparent or translucent and colorless, and various binders are known, and these can be used in the present invention. Examples include acrylic resins such as polyacrylonitrile, polyacrylic acid esters and polyacrylamide, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, Modified cellulose resins such as methylcellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, etc. Cellulose resins such as nitrocellulose, ethylhydroxyethylcellulose and ethylcellulose, polyurethane resins, polyamide resins, polyester resins, polycarbonate resins, phenoxy Resin, phenolic resin, epoxy resin, various elastomers Etc. The. The polymer can also be crosslinked with various crosslinking agents.

(Copolymer (a))
The copolymer (a) used as a resin binder for the dye layer of the present invention will be described.
The copolymer (a) used in the dye layer of the present invention is an α-olefin residue unit represented by the above formula (i): an N-phenyl-substituted maleimide residue unit represented by the above formula (ii) = 49: 51 to 35:65 (hereinafter, molar ratio), preferably 45:55 to 35:65.
The weight average molecular weight of the copolymer (a) is preferably 5 × 10 ^{3 to} 5 × 10 ⁶ in terms of standard polystyrene. Here, the mass average molecular weight can be measured by using an elution curve of the copolymer (a) by gel permeation chromatography (hereinafter referred to as GPC) as a standard polystyrene equivalent value. And when the polystyrene equivalent mass average molecular weight of the copolymer (a) is 5 × 10 ³ or more, it is preferable because it has sufficient dye storage stability, and when the mass average molecular weight is 5 × 10 ⁶ or less, sufficient It is preferable because it has transferability.
Moreover, when the molar ratio of the α-olefin residue unit represented by the formula (i) is 35 or more, it is preferable because of sufficient transferability. On the other hand, when the molar ratio is 49 or less, it is preferable because it has sufficient dye storage stability.

R ¹ , R ² and R ³ in the α-olefin residue unit represented by the formula (i) constituting the copolymer (a) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 2- A pentyl group, n-hexyl group, 2-hexyl group, etc. can be mentioned. Here, when R ¹ , R ² , and R ³ are alkyl substituents having 6 or less carbon atoms, the glass transition temperature of the copolymer is sufficiently high, and the dye storage stability is also sufficiently high, which is preferable.
As specific compounds for deriving the α-olefin residue unit represented by the formula (i), for example, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1- Hexene, 2-methyl-1-heptene, 1-isooctene, 2-methyl-1-octene, 2-ethyl-1-pentene, 2-methyl-2-pentene, 2-methyl-2-hexene, ethylene, propylene, 1-butene, 1-hexene and the like can be mentioned, among which α-olefins belonging to 1,2-disubstituted olefins are preferable, and in particular, a copolymer (a) excellent in heat resistance, transparency and mechanical properties can be obtained. Therefore, isobutene is preferable. The α-olefin residue unit may be one or a combination of two or more, and the ratio is not particularly limited.

The N-phenyl substitution in the N-phenyl substituted maleimide residue represented by the formula (ii) constituting the copolymer (a) refers to a group in which an unsubstituted phenyl group or a substituted phenyl group is introduced as an N substituent.
R ⁴ and R ⁵ in the N-phenyl-substituted maleimide residue unit represented by the formula (ii) constituting the copolymer (a) are each independently a hydrogen atom or a linear or branched group having 1 to 8 carbon atoms. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms are alkyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert. -Butyl group, n-pentyl group, 2-pentyl group, n-hexyl group, 2-hexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-octyl group, 3 -An octyl group etc. can be mentioned. When the carbon number of the alkyl group is 8 or less, the glass transition temperature of the copolymer is high and the dye storage stability is also high. R ⁴ and R ⁵ are preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group or n-butyl group, more preferably a hydrogen atom, methyl group or ethyl group, More preferred are a hydrogen atom and a methyl group.
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group or a salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, a cyano group, a nitro group or A linear or branched alkyl group having 1 to 8 carbon atoms, and examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom. Examples of the alkoxycarbonyl group include methoxycarbonyl. Group, ethoxycarbonyl group and the like, examples of the aryloxycarbonyl group include phenoxycarbonyl group, and examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert-butyl group, -Pentyl group, 2-pentyl group, n-hexyl group, 2-hexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-octyl group, 3-octyl group, etc. Can be mentioned. When the carbon number of the alkyl group is 8 or less, the glass transition temperature of the copolymer is high and the dye storage stability is also high. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. It is.

  Examples of the compound for deriving the N-phenyl substituted maleimide residue unit represented by the formula (ii) include maleimide compounds in which an unsubstituted phenyl group or a substituted phenyl group is introduced as the N substituent of the maleimide compound. Specifically, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2-ethylphenyl) maleimide, N- (2-n-propylphenyl) maleimide, N- (2-isopropylphenyl) maleimide, N- (2-n-butylphenyl) maleimide, N- (2-s-butylphenyl) maleimide, N- (2-tert-butylphenyl) maleimide, N- (2-n-pentylphenyl) maleimide, N- (2-tert-pentylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6 -Diethylphenyl) maleimide, N- (2,6-di-n-propylphenyl) maleimide, N- (2,6-di-isopropylphenyl) maleimide, N- (2-methyl, 6-ethylphenyl) maleimide, N- (2-methyl, 6-isopropylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N- (2-bromophenyl) maleimide, N- (2,6-dichlorophenyl) maleimide, N- (2,6 -Dibromophenyl) maleimide, N-2-biphenylmaleimide, N-2-diphenylethermaleimide, N- (2-cyanophenyl) maleimide, N- (2-nitrophenyl) maleimide, N- (2,4,6-trimethyl) Phenyl) maleimide, N- (2,4-dimethylphenyl) maleimide, N-perbromophenyl Reimido, N-(2-methyl, 4-hydroxyphenyl) maleimide, N-(2,6-diethyl, 4-hydroxyphenyl) maleimide and the like. Among them, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2-ethylphenyl) maleimide, N- (2-n-propylphenyl) maleimide, N- (2-isopropylphenyl) maleimide, N -(2-n-butylphenyl) maleimide, N- (2-s-butylphenyl) maleimide, N- (2-tert-butylphenyl) maleimide, N- (2-n-pentylphenyl) maleimide, N- ( 2-tert-pentylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2,6-di-n-propylphenyl) maleimide, N -(2,6-di-isopropylphenyl) maleimide, N- (2-methyl, 6-ethylphenyl) maleimide, N- (2-methyl) , 6-isopropylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N- (2-bromophenyl) maleimide, N- (2,6-dichlorophenyl) maleimide, N- (2,6-dibromophenyl) maleimide N-2-biphenylmaleimide, N-2-diphenylethermaleimide, N- (2-cyanophenyl) maleimide, and N- (2-nitrophenyl) maleimide are preferable, and particularly excellent in heat resistance, transparency, and mechanical properties. N-phenylmaleimide and N- (2-methylphenyl) maleimide are more preferable because the polymer (a) is obtained. The N-phenyl-substituted maleimide residue unit may be one or a combination of two or more, and the ratio is not particularly limited.

  As the copolymer (a), a compound that derives an α-olefin residue unit represented by the above formula (i) and a compound that derives an N-phenyl-substituted maleimide residue unit represented by the formula (ii) are known. It can be obtained by utilizing a polymerization method. Examples of known polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Further, as another method, a copolymer obtained by copolymerizing a compound that induces the α-olefin residue unit represented by the above formula (i) and maleic anhydride is further added to, for example, aniline, 2- It can also be obtained by reacting aniline having a substituent introduced at the 6-position and performing a dehydration ring-closing imidization reaction.

  The copolymer (a) is a copolymer comprising an α-olefin residue unit represented by the above formula (i) and an N-phenyl-substituted maleimide residue unit represented by the formula (ii). -Phenylmaleimide-isobutene copolymer, N-phenylmaleimide-ethylene copolymer, N-phenylmaleimide-2-methyl-1-butene copolymer, N- (2-methylphenyl) maleimide-isobutene copolymer, N- (2-methylphenyl) maleimide-ethylene copolymer, N- (2-methylphenyl) maleimide-2-methyl-1-butene copolymer, N- (2-ethylphenyl) maleimide-isobutene copolymer N- (2-ethylphenyl) maleimide-ethylene copolymer, N- (2-ethylphenyl) maleimide-2-methyl-1-butene copolymer Among them, N-phenylmaleimide-isobutene copolymer and N- (2-methylphenyl) maleimide-isobutene copolymer are particularly excellent in heat resistance, transparency, and mechanical properties. preferable.

(Acrylonitrile-styrene copolymer (b))
The acrylonitrile-styrene copolymer (b) preferably used in the present invention is an acrylonitrile residue unit: styrene residue unit = 36: 64 to 50:50 (hereinafter referred to as “mass ratio”), particularly a resin having excellent compatibility and toughness. It is preferably 37:63 to 50:50 because a composition and a film can be obtained.
The mass average molecular weight of the acrylonitrile-styrene copolymer (b) is preferably 5 × 10 ^{3 to} 5 × 10 ⁶ in terms of standard polystyrene. Here, the mass average molecular weight can be measured by using an elution curve of acrylonitrile-styrene copolymer by GPC as a standard polystyrene equivalent value. And when the polystyrene equivalent weight average molecular weight of the acrylonitrile-styrene copolymer is less than 5 × 10 ³ , the dye storage stability is lowered, and when it exceeds 5 × 10 ⁶ , the transferability is lowered.
Further, in the acrylonitrile-styrene copolymer, it is preferable that the mass ratio of the acrylonitrile residue unit is 36 or more because it has sufficient transferability. On the other hand, an acrylonitrile residue unit having a mass ratio of 50 or less is preferable because it has sufficient dye storage stability.
As the acrylonitrile-styrene copolymer (b) used in the present invention, an acrylonitrile-styrene copolymer in which some or all of the styrene residue units are α-methylstyrene residue units can also be used.

  As a method for synthesizing the acrylonitrile-styrene copolymer (b) preferably used in the present invention, a known polymerization method can be used, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or the like. It is possible. Moreover, what was obtained as a commercial item may be used.

(Structure of dye layer)
In addition to containing at least the copolymer (a) having the above structure, the dye layer of the present invention preferably has the following characteristics.
In the dye layer of the present invention, it is preferred that yellow, magenta, and cyan dye layers and, if necessary, a black dye layer are repeatedly coated on the same support in the surface order. As an example, the case where the dye layers of yellow, magenta, and cyan hues are separately applied in the surface direction in accordance with the area of the recording surface of the thermal transfer image-receiving sheet in the major axis direction of the same support. Can do. In addition to these three layers, it is also a preferred embodiment that either the dye layer of black hue or the laminate of the transferable protective layer or both are separately applied.
When taking such an aspect, it is also a preferable aspect to provide a mark on the thermal transfer ink sheet for the purpose of transmitting the starting point of each color to the printer. Thus, by repeating the coating sequentially in the surface order, it is possible to form an image by transferring a dye, and further laminate a protective layer on the image with a single thermal transfer ink sheet.
However, the present invention is not limited to the method of providing the dye layer as described above. Sublimation type thermal transfer dye layer and thermal melt transfer dye layer (ink layer) can be provided side by side, and it is also possible to make changes such as providing dye layers with hues other than yellow, magenta, cyan and black. is there. Also, the form may be long or a single-wafer thermal transfer sheet.

  The dye layer may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the composition of each layer constituting the dye layer may be the same or different.

  The dye ink for forming the dye layer contains a dye, preferably a sublimable dye and a binder resin. Furthermore, if necessary, waxes, silicone resins, fluorine-containing organic compounds and the like can be contained.

Each dye is preferably contained in the dye layer in an amount of 10 to 90% by mass (solid content), more preferably 20 to 80% by mass.
The dye layer is applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating. The coating amount of the dye layer is preferably 0.1 to 2.0 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). Is 0.2 to 1.2 g / m ² . The film thickness of the dye layer is preferably from 0.1 to 2.0 μm, more preferably from 0.2 to 1.2 μm.

(dye)
The dye used in the present invention is not particularly limited as long as it is diffused by heat and can be incorporated into the thermal transfer ink sheet, and can be transferred from the thermal transfer ink sheet to the thermal transfer image receiving sheet by heating. As the dye, a conventionally used dye or a known dye can be used.
Preferred dyes include, for example, methine series such as diarylmethane series, triarylmethane series, thiazole series, and merocyanine, indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, and azomethine series represented by pyridone azomethine. Cyanomethylene, thiazine, azine, acridine, benzeneazo, pyridoneazo, thiophenazo, isothiazoleazo, pyrroleazo, pyralazo, imidazoleazo, thiadiazole, typified by xanthene, oxazine, dicyanostyrene, tricyanostyrene Azos such as azo, triazole azo, and dizazo, 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.

  Hereinafter, the pigments (dyes) represented by the general formulas (Y1) to (Y9), (M1) to (M8), and (C1) to (C4) that can be preferably used in the present invention will be described in detail. .

In general formula (Y1), A represents a substituted or unsubstituted benzene ring, and R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents a substituted aryl group, and R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted Represents an alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted carbamoyl group, and R ⁴ represents a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl Represents a group.

Examples of the substituent that each group of A, R ¹ , R ² , R ³ and R ⁴ may be substituted include a halogen atom, an unsaturated aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxy group ( (Typically alkoxy group), acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, aliphatic oxycarbonylamino Group (typically alkoxycarbonylamino group), sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), sulfamoyl group, aliphatic (typically alkyl) Or arylsulfinyl group), aliphatic (as representative Alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo group, imide group, hydroxyl group, cyano group, nitro group , Sulfo group, carboxyl group and the like.

  Each of these groups may further have a substituent, and examples of such a substituent include the above-described substituents.

A preferable combination of substituents of the dye represented by the general formula (Y1) is that A is a substituted or unsubstituted benzene ring, and R ¹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ² is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. R ³ is a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted carbon group having 6 to 10 carbon atoms. A combination that is an aryl group.
A more preferable combination of substituents is that A is a substituted or unsubstituted benzene ring, R ¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, R ² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, and R ³ is a substituted or unsubstituted amino group or a substituted or unsubstituted alkoxy group. , R ⁴ is a combination of a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted phenyl group.
The most preferred combination of substituents is that A is a methyl group or a benzene ring substituted with a chlorine atom or an unsubstituted benzene ring, and R ¹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or an allyl group. R ² is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or an allyl group, R ³ is a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, and R ⁴ is substituted or unsubstituted A combination that is an unsubstituted phenyl group.

In general formula (Y2), R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R ⁶ and R ⁷ each independently represents a substituted or unsubstituted alkyl group, R ⁸ Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, and R ⁹ represents a substituted or unsubstituted alkyl group, substituted or unsubstituted. Represents an aryl group.

Each group of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may further have a substituent. The substituents that each group of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be substituted are each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). Is the same as the substituent which may be substituted.

A preferred combination of substituents of the dye represented by formula (Y2) is as follows: R ⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an allyl group, and R ⁶ is a substituted or unsubstituted carbon number. An alkyl group having 1 to 8 carbon atoms, R ⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁸ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted. An aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, and R ⁹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted carbon; A combination which is an aryl group of several 6 to 10.
More preferable combinations of substituents are as follows: R ⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an allyl group; R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; ⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group , A substituted or unsubstituted amino group, and R ⁹ is a combination of a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted phenyl group.
In the most preferable combination of substituents, R ⁵ is an unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁶ is an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁷ is an unsubstituted carbon number. 1 to 4 alkyl groups, R ⁸ is a methoxy group, an ethoxy group, and a dimethylamino group, and R ⁹ is an unsubstituted phenyl group.

In general formula (Y3), R ¹⁰ represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ¹¹ represents a hydrogen atom or a halogen atom, and R ¹² represents a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. An aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group.
Each group of R ¹⁰ and R ¹² may further have a substituent. The substituent that each group of R ¹⁰ and R ¹² may be substituted is the substituent that each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted with The same.

A preferable combination of substituents of the dye represented by the general formula (Y3) is that R ¹⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ¹¹ is a hydrogen atom, a chlorine atom, or bromine. And a combination in which R ¹² is an unsubstituted alkoxycarbonyl group, an unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted carbamoyl group.
A more preferable combination of substituents is that R ¹⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹¹ is a hydrogen atom or a bromine atom, and R ¹² is an unsubstituted carbon number of 2 A combination of 10 to 10 alkoxycarbonyl groups and 2 to 12 carbon dialkylcarbamoyl groups.
The most preferable combination of substituents is that R ¹⁰ is a hydrogen atom, an unsubstituted alkyl group having 2 to 4 carbon atoms, R ¹¹ is a hydrogen atom, and R ¹² is a dialkylcarbomoyl group having 2 to 10 carbon atoms. It is a certain combination.

In general formula (Y4), B represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, R ¹³ represents a substituted or unsubstituted alkyl group, and R ¹⁴ represents a substituted or unsubstituted group. Represents an alkyl group or a substituted or unsubstituted aryl group.

Each group of B, R ¹³ and R ¹⁴ may further have a substituent. The substituent which each group of B, R ¹³ and R ¹⁴ may be substituted is a substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted. Same as group.

Preferred substituent combinations of the dye represented by the general formula (Y4) are as follows: B is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted thiadiazolyl group. R ¹³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. A combination that is a group.
More preferred substituent combinations of the substituents are such that B is a substituted or unsubstituted phenyl group, a substituted or unsubstituted 1,3,4-thiadiazolyl group, and R ¹³ is a substituted or unsubstituted carbon number of 1-6. And a combination in which R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group.
The most preferable combination of the substituents of the substituents is a 1,3,4-thiadiazolyl group in which B is a 4-nitrophenyl group and a thioalkyl group having 1 to 6 carbon atoms, and R ¹³ is an unsubstituted carbon number of 1 Or a combination of R ¹⁴ is an unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group.

In the general formula (Y5), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Each group of R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may further have a substituent. The substituents which each group of R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be substituted are the groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be.

A preferable combination of substituents of the dye represented by the general formula (Y5) is R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. , A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ¹⁸ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms It is.
A more preferred combination of substituents is that R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ¹⁷ is substituted. Alternatively, it is an unsubstituted phenyl group, and a combination in which R ¹⁸ is a substituted or unsubstituted phenyl group.
The most preferred combination of substituents is that R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ¹⁷ is unsubstituted. The combination is a substituted phenyl group and R ¹⁸ is an unsubstituted phenyl group.

  In general formula (Y6), C, D, and E each independently represent a substituted or unsubstituted benzene ring.

Each group of C, D and E may further have a substituent. The substituent that each group of C, D, and E may be substituted is the substituent that each group of A, R ¹ , R ² , R ^3, and R ^{4 in} the general formula (Y1) may be substituted. The same.

  C is preferably a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 8 carbon atoms, a benzene ring substituted with a hydroxyl group, or an unsubstituted benzene ring, More preferably, it is a benzene ring substituted by an alkyl group having 1 to 6 carbon atoms, a benzene ring substituted by an alkoxy group having 1 to 6 carbon atoms, or a benzene ring substituted by a hydroxyl group, most preferably 1 to 4 carbon atoms. A benzene ring substituted with an alkyl group and a benzene ring substituted with an alkoxy group having 1 to 4 carbon atoms.

  D is preferably a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms or an unsubstituted benzene ring, more preferably a benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, or an unsubstituted benzene ring A ring, most preferably a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms, or an unsubstituted benzene ring.

  E is preferably a benzene ring substituted with a hydroxyl group and an alkyl group having 1 to 8 carbon atoms or a benzene ring substituted with a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms, more preferably a hydroxyl group and 1 carbon atom. A benzene ring or hydroxyl group substituted with an alkyl group of ˜6 and a benzene ring substituted with an alkoxy group of 1 to 6 carbon atoms, preferably a benzene ring or hydroxyl group substituted with a hydroxyl group and an alkyl group of 1 to 4 carbon atoms And a benzene ring substituted with an alkoxy group having 1 to 4 carbon atoms.

In general formula (Y7), F represents a substituted or unsubstituted benzene ring, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents a substituted aryl group.

Each group of F, R ¹⁹ and R ²⁰ may further have a substituent. The substituent which each group of F, R ¹⁹ and R ²⁰ may be substituted is a substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted. Same as group.

A preferable combination of substituents of the dye represented by the general formula (Y7) is that F is a substituted or unsubstituted benzene ring, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. It is a certain combination.
More preferable combinations of substituents are such that F is a substituted or unsubstituted benzene ring, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, A combination in which R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, or a substituted or unsubstituted phenyl group.
The most preferred combination of substituents is F is a benzene ring substituted with a methyl group, R ¹⁹ is an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ²⁰ is a substituted alkyl group having 1 to 4 carbon atoms. A combination that is a group.

In general formula (Y8), G represents a substituted or unsubstituted benzene ring, and R ²¹ and R ²² each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Each group of G, R ²¹ and R ²² may further have a substituent. The substituent which each group of G, R ²¹ and R ²² may be substituted is a substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted. Same as group.

A preferred combination of substituents of the dye represented by formula (Y8) is that G is a benzene ring having a substituent, R ²¹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, R ²² Is a combination in which is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
A more preferable combination of substituents is that G is a benzene ring substituted with a substituted or unsubstituted alkoxycarbonyl group, R ²¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ²² is substituted. Or it is a combination which is an unsubstituted C1-C6 alkyl group.
The most preferred combination of substituents is that G is a benzene ring substituted by a substituted or unsubstituted alkoxycarbonyl group, R ²¹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ²² is substituted. Or it is the combination which is an unsubstituted C1-C4 alkyl group.

In the general formula (Y9), R ²³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group.

R ²³ may further have a substituent. The substituent which R ²³ may be substituted is the same as the substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may substitute.

R ²³ is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an allyl group, more preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an allyl group, and most preferably A substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and an allyl group.

In general formula (M1), H is a substituted or unsubstituted benzene ring or a substituted or unsubstituted pyridine ring, and R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group.

Each group of H, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may further have a substituent. The substituents that each group of H, R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be substituted are the groups of A, R ¹ , R ² , R ^3, and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be substituted.

A preferable combination of substituents of the dye represented by the general formula (M1) is that H is an unsubstituted benzene ring, R ²⁴ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 10 carbon atoms, R ²⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ²⁶ is substituted or unsubstituted. A substituted alkyl group having 1 to 8 carbon atoms and an allyl group, and R ²⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group.
More preferable combinations of substituents are such that H is an unsubstituted benzene ring, R ²⁴ is a substituted or unsubstituted phenyl group, R ²⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, A combination in which R ²⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ²⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
The most preferable combination of substituents is that H is an unsubstituted benzene ring, R ²⁴ is a 2-chlorophenyl group, R ²⁵ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ²⁶ is The combination is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ²⁷ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

In the general formula (M2), I is a substituted or unsubstituted benzene ring or a substituted or unsubstituted pyridine ring, and R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group.

Each group of I, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may further have a substituent. The substituents which each group of I, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be substituted are the groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be substituted.

A preferable combination of substituents of the dye represented by the general formula (M2) is that I is a substituted or unsubstituted pyridine ring or an unsubstituted benzene ring, and R ²⁸ is a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms. An alkyl group, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ²⁹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Yes, R ³⁰ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group, and R ³¹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group.
A more preferable combination of substituents is that I is a substituted or unsubstituted pyridine ring or an unsubstituted benzene ring, R ²⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ²⁹ is substituted or unsubstituted. An unsubstituted alkyl group having 1 to 6 carbon atoms, R ³⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. It is a certain combination.
The most preferred combination of substituents is that in which I is a substituted or unsubstituted pyridine ring or an unsubstituted benzene ring, and R ²⁸ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ²⁹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R ³⁰ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ³¹ is a substituted or unsubstituted carbon number. A combination of 1 to 4 alkyl groups.

In general formula (M3), J represents a substituted or unsubstituted benzene ring, and R ³² , R ³³ and R ³⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents a substituted aryl group.

Each group of J, R ³² , R ³³ and R ³⁴ may further have a substituent. The substituents that each group of J, R ³² , R ³³ and R ³⁴ may be substituted are those in which groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) are substituted. It is the same as a good substituent.

A preferable combination of substituents of the dye represented by the general formula (M3) is a benzene ring in which J is substituted with an acylamino group having 2 to 8 carbon atoms, and R ³² is a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms. R ³³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group, and R ³⁴ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group. Is a combination.
A more preferable combination of substituents is that J is a benzene ring substituted with an acylamino group having 2 to 6 carbon atoms, R ³² is a substituted or unsubstituted alkyl group or acyl group having 1 to 6 carbon atoms, and R ³³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and an allyl group, and R ³⁴ is a combination of a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and an allyl group.
The most preferred combination of substituents is a benzene ring in which J is substituted with an acylamino group having 2 to 4 carbon atoms, R ³² is a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms or an acyl group, R ³³ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and an allyl group, and R ³⁴ is a combination of a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and an allyl group.

In general formula (M4), K is a substituted or unsubstituted benzene ring, and R ³⁵ , R ³⁶ and R ³⁷ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents a substituted aryl group.

Each group of K, R ³⁵ , R ³⁶ and R ³⁷ may further have a substituent. The substituents which each group of K, R ³⁵ , R ³⁶ and R ³⁷ may be substituted are those in which groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) are substituted. It is the same as a good substituent.

A preferable combination of substituents of the dye represented by formula (M4) is a benzene ring in which K is substituted with an acylamino group having 2 to 8 carbon atoms, and R ³⁵ is a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms. R ³⁶ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group, and R ³⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and an allyl group It is.
A more preferable combination of substituents is a benzene ring in which K is substituted with an acylamino group having 2 to 6 carbon atoms, R ³⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³⁶ is substituted. Alternatively, it is an unsubstituted alkyl group having 1 to 6 carbon atoms or an allyl group, and R ³⁷ is a combination of a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an allyl group.
The most preferable combination of substituents is a benzene ring in which K is substituted with an acylamino group having 2 to 4 carbon atoms, R ³⁵ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ³⁶ is substituted. Alternatively, it is an unsubstituted alkyl group having 1 to 4 carbon atoms or an allyl group, and R ³⁷ is a combination of a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or an allyl group.

In the general formula (M5), R ³⁸ and R ³⁹ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ⁴⁰ and R ⁴¹ are independently Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Each group of R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ may further have a substituent. The substituents which each group of R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ may be substituted are the groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be.

In the preferable combination of substituents of the dye represented by the general formula (M5), R ³⁸ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. R ³⁹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ⁴⁰ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. , A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ⁴¹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms It is.
A more preferable combination of substituents is that R ³⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group, and R ³⁹ is substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A group, a substituted or unsubstituted phenyl group, R ⁴⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁴¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms It is.
The most preferable combination of substituents is that R ³⁸ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted phenyl group, and R ³⁹ is substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. A group, a substituted or unsubstituted phenyl group, R ⁴⁰ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁴¹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms It is.

In the general formula (M6), R ⁴² is a substituted or unsubstituted aryloxy group, R ⁴³ is a hydrogen atom, a substituted or unsubstituted aryloxy group, R ⁴⁴ represents a hydroxyl group, a substituted or unsubstituted amino It is a group. )

Each group of R ⁴² and R ⁴³ may further have a substituent. The substituent that each group of R ⁴² and R ⁴² may be substituted is the substituent that each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted with The same.

A preferable combination of substituents of the dye represented by the general formula (M6) is that R ⁴² is a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, R ⁴³ is a hydrogen atom, substituted or unsubstituted carbon. It is an aryloxy group of several 6 to 10, and a combination in which R ⁴⁴ is a hydroxyl group or an unsubstituted amino group.
A more preferred combination is a combination in which R ⁴² is a substituted or unsubstituted phenoxy group, R ⁴³ is a hydrogen atom, a substituted or unsubstituted phenoxy group, and R ⁴⁴ is a hydroxyl group or an unsubstituted amino group. is there.
The most preferred combination is that R ⁴² is a phenoxy group or an unsubstituted phenoxy group substituted with a substituted or unsubstituted amino group, R ⁴³ is a hydrogen atom, a substituted or unsubstituted phenoxy group, and R ⁴⁴ is a hydroxyl group. Or a combination that is an unsubstituted amino group.

In general formula (M7), L represents a substituted or unsubstituted benzene ring, and R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Represents a substituted aryl group.

Each group of L, R ⁴⁵ and R ⁴⁶ may further have a substituent. The substituent which each group of L, R ⁴⁵ and R ⁴⁶ may be substituted is a substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted. Same as group.

A preferred combination of substituents of the dye represented by the general formula (M7) is such that L is a substituted or unsubstituted benzene ring, R ⁴⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ⁴⁶ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. It is a certain combination.
More preferable combinations of substituents are such that L is a substituted or unsubstituted benzene ring, R ⁴⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, A combination in which R ⁴⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, or a substituted or unsubstituted phenyl group.
The most preferred combination of substituents is that L is a benzene ring substituted with a methyl group, R ⁴⁵ is an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ is a substituted alkyl group having 1 to 4 carbon atoms. A combination that is a group.

In general formula (M8), Q represents a substituted or unsubstituted benzene ring, R ¹⁰⁰ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted. R ¹⁰¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R ¹⁰² and R ¹⁰³ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; It represents a substituted alkenyl group or a substituted or unsubstituted aryl group. )

Each group of Q, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may further have a substituent. The substituents that each group of Q, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be substituted are the groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be substituted.

A preferable combination of substituents of the dye represented by the general formula (M8) is that Q is a substituted or unsubstituted benzene ring, and R ¹⁰² is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, A substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ¹⁰³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. R ¹⁰⁰ is a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, and R ¹⁰¹ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted carbon group having 6 to 10 carbon atoms. A combination that is an aryl group.
A more preferred combination is that Q is a substituted or unsubstituted benzene ring, R ¹⁰² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, and R ¹⁰³ is A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an allyl group, a substituted or unsubstituted phenyl group, R ¹⁰⁰ is a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, and R ¹⁰¹ Is a combination of a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted phenyl group.
The most preferred combination is that Q is a substituted or unsubstituted benzene ring, R ¹⁰² is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or an allyl group, and R ¹⁰³ is a substituted or unsubstituted carbon number of 1 A combination of ˜4 alkyl groups and allyl groups, R ¹⁰⁰ is a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, and R ¹⁰¹ is a substituted or unsubstituted phenyl group.

In general formula (C1), M represents a substituted or unsubstituted benzene ring, R ⁴⁷ represents a hydrogen atom or a halogen atom, R ⁴⁸ represents a substituted or unsubstituted alkyl group, and R ⁴⁹ represents substituted or unsubstituted. And R ⁵⁰ and R ⁵¹ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. .

Each group of M, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ and R ⁵¹ may further have a substituent. The substituents that each group of M, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ and R ⁵¹ may be substituted are the groups A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1). It is the same as the substituent which may be substituted.

A preferable combination of substituents of the dye represented by the general formula (C1) is a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms, a benzene ring substituted with a chlorine atom, or an unsubstituted benzene ring, R ⁴⁷ is a hydrogen atom, a chlorine atom or a bromine atom; R ⁴⁸ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; R ⁴⁹ is a substituted or unsubstituted acylamino group having 2 to 10 carbon atoms; A substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, R ⁵⁰ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁵¹ is a substituted or unsubstituted carbon group having 1 to 8 carbon atoms. It is a combination which is an alkyl group.
More preferable combinations of substituents are a benzene ring and an unsubstituted benzene ring in which M is an alkyl group having 1 to 2 carbon atoms, R ⁴⁷ is a hydrogen atom or a chlorine atom, and R ⁴⁸ is substituted or unsubstituted. R ⁴⁹ is a substituted or unsubstituted acylamino group having 2 to 8 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 8 carbon atoms, and R ⁵⁰ is The combination is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁵¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
The most preferred combination is a preferred substituent group wherein M is a benzene ring substituted with a methyl group or an unsubstituted benzene ring, R ⁴⁷ is a hydrogen atom or a chlorine atom, and R ⁴⁸ is a substituted or unsubstituted carbon number. An alkyl group having 1 to 6 carbon atoms, R ⁴⁹ is a substituted or unsubstituted acylamino group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 6 carbon atoms, and R ⁵⁰ is a substituted or unsubstituted alkyl group. It is a substituted alkyl group having 1 to 4 carbon atoms, and R ⁵¹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

In general formula (C2), T represents a substituted or unsubstituted benzene ring, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group. R ⁵³ and R ⁵⁴ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Each group of T, R ⁵² , R ⁵³ and R ⁵⁴ may further have a substituent. The substituents that each group of T, R ⁵² , R ⁵³ and R ⁵⁴ may be substituted are those in which groups of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) are substituted. It is the same as a good substituent.

A preferred combination of substituents of the dye represented by the general formula (C2) includes a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 8 carbon atoms, and unsubstituted. Wherein R ⁵² is a hydrogen atom, a substituted or unsubstituted acylamino group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms. It is a carbamoyl group, R ⁵³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁵⁴ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
More preferable combinations of substituents are a benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 6 carbon atoms, and an unsubstituted benzene ring, and R ⁵² is hydrogen. An atom, a substituted or unsubstituted acylamino group having 2 to 8 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 8 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 8 carbon atoms, and R ⁵³ is substituted or The combination is an unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁵⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. The most preferred combination of substituents is a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted benzene ring, and R ⁵² is hydrogen. An atom, a substituted or unsubstituted acylamino group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 6 carbon atoms, and R ⁵³ is substituted or The combination is an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁵⁴ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

In general formula (C3), R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Each group of R ⁵⁵ and R ⁵⁶ may further have a substituent. The substituent which each group of R ⁵⁵ and R ⁵⁶ may be substituted is the substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted with The same.

In the preferable combination of substituents of the dye represented by the general formula (C3), R ⁵⁵ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. , R ⁵⁶ 'is a combination which is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
A more preferable combination of substituents is that R ⁵⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group, and R ⁵⁶ is substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A combination that is a group, a substituted or unsubstituted phenyl group.
The most preferred combination of substituents is R ⁵⁵ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁵⁶ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted phenyl A combination that is a group.

In general formula (C4), U represents a substituted or unsubstituted benzene ring, and R ⁵⁶ and R ⁵⁸ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl It is a group.

Each group of U, R ⁵⁶ and R ⁵⁷ may further have a substituent. The substituent which each group of U, R ⁵⁶ and R ⁵⁷ may be substituted is a substituent which each group of A, R ¹ , R ² , R ³ and R ^{4 in} the general formula (Y1) may be substituted. Same as group.

A preferred combination of substituents of the dye represented by the general formula (C4) includes a benzene ring substituted with an alkyl group having 1 to 8 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 8 carbon atoms, and unsubstituted. In which R ⁵⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and R ⁵⁸ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
A more preferable combination is a benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted benzene ring, and R ⁵⁷ is substituted or unsubstituted. And a combination in which R ⁵⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
The most preferred combination is a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms, a benzene ring substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted benzene ring, and R ⁵⁷ is substituted or unsubstituted. And a combination in which R ⁵⁸ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

  Specific examples of the compounds represented by formulas (Y1) to (Y9), (M1) to (M8), and (C1) to (C4) that can be preferably used in the present invention are shown below. The dyes of the general formulas (Y1) to (Y9), (M1) to (M8), and (C1) to (C4) used in the present invention are not limitedly interpreted by the following specific examples.

[Dye barrier layer]
In the heat-sensitive transfer sheet of the present invention, a dye barrier layer can be provided between the dye layer and the support.

[Easy Adhesion Treatment / Easily Adhesive Layer]
An easy adhesion treatment may be performed on the support surface for the purpose of improving the wettability and adhesion of the coating solution. Treatment methods include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, primer treatment, grafting treatment and other known resin surface modifications. Quality technology can be illustrated.
Moreover, an easily bonding layer can also be formed on a support body by application. Examples of the resin used for the easy-adhesion layer include polyester resins, polyacrylate resins, polyvinyl acetate resins, vinyl resins such as polyvinyl chloride resins and polyvinyl alcohol resins, and polyvinyl resins such as polyvinyl acetoacetal and polyvinyl butyral. Examples include acetal resins, polyether resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, polystyrene resins, polyethylene resins, polypropylene resins, and the like.
When the film used for the support is melt-extruded and formed, the unstretched film may be subjected to a coating treatment and then stretched.
In addition, two or more kinds of the above treatments can be used in combination.

[Transferable protective layer laminate]
The transferable protective layer laminate generally refers to a laminate comprising a protective layer, a release layer, and an adhesive layer.
In the present invention, it is preferable to provide a transferable protective layer laminate in the surface order 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, and has durability such as scratch resistance, light resistance, and weather resistance. The purpose is to improve performance. This is effective when image durability such as light resistance, scratch resistance and chemical resistance is insufficient if the transferred dye is exposed to the surface of the image receiving sheet.
The transferable protective layer laminate can be formed on the support in the order of the release layer, the protective layer, and the adhesive layer 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.

[Protective layer]
The resin forming the protective layer of the present invention is preferably a resin excellent in scratch resistance, chemical resistance, transparency and hardness, such as polyester resin, acrylic resin, polystyrene resin, polyurethane resin, acrylic urethane resin, and these resins. Silicone-modified resins, ultraviolet blocking resins, mixtures of these resins, ionizing radiation curable resins, ultraviolet curable resins, and the like can be used. Of these, polyester resins and acrylic resins are preferable.
It is also possible to crosslink with various crosslinking agents.

The acrylic resin is a polymer composed of at least one monomer selected from conventionally known acrylate monomers and methacrylate monomers, and may be copolymerized with styrene, acrylonitrile or the like in addition to the acrylic monomer. As a preferred monomer, methyl methacrylate is charged and contained in an amount of 50% by mass or more.
The acrylic resin of the present invention preferably has a molecular weight of 20,000 to 100,000. If it is less than 20,000, an oligomer is produced at the time of synthesis and stable performance cannot be obtained. If it exceeds 100,000, the foil breakage is deteriorated during transfer of the protective layer.

  As the polyester resin of the present invention, conventionally known saturated polyester resins can be used. When the polyester resin is used, the glass transition temperature is preferably 50 to 120 ° C., the molecular weight is preferably in the range of 2,000 to 40,000, and further in the range of 4,000 to 20,000. Sometimes the foil breakability is improved, which is more preferable.

(UV absorber)
The protective layer can contain an ultraviolet absorber, and as the ultraviolet absorber, conventionally known inorganic ultraviolet absorbers and organic ultraviolet absorbers can be used. Examples of organic UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, triazine-based, substituted acrylonitrile-based, hindered amine-based non-reactive UV absorbers, and non-reactive UV absorbers such as, for example, Introducing an addition polymerizable double bond such as vinyl group, acryloyl group or methacryloyl group, or alcoholic hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group, etc. A polymerized or grafted product can be used. In addition, a method is disclosed in which a UV absorber is dissolved in a resin monomer or oligomer and then the monomer or oligomer is polymerized (Japanese Patent Application Laid-Open No. 2006-21333), and thus obtained UV blocking resin is used. You can also In this case, the ultraviolet absorber may be non-reactive.
Among these ultraviolet absorbers, benzophenone, benzotriazole, and triazine are particularly preferable. These UV absorbers are preferably used in combination so as to cover the effective UV absorption wavelength range according to the characteristics of the dye used for image formation. In the case of non-reactive UV absorbers, UV absorbers are used. It is preferable to use a mixture of a plurality of different structures so that the agent does not precipitate.
Commercially available UV absorbers include Tinuvin-P (manufactured by Ciba Geigy), JF-77 (manufactured by Johoku Chemical), Sea Soap 701 (manufactured by Shiroishi Calcium), Sumisop 200 (manufactured by Sumitomo Chemical), Biosoap 520 (manufactured by Kyodo Yakuhin) , ADK STAB LA-32 (manufactured by Asahi Denka) and the like.

  By using an ionizing radiation curable resin or an ultraviolet 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.

(Filler)
A filler can also be preferably used for the protective layer. 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 silica fine particles. It can be illustrated. In the thermal transfer 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 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.

  Although the formation method of a protective layer depends on the kind of resin used, it is formed by the method similar to the formation method of the said dye layer, and the thickness of 0.5-10 micrometers is preferable.

[Release layer]
In the transferable protective layer laminate, a release layer can be formed between the support and the protective layer when the protective layer is difficult to peel from the support during thermal transfer. A release layer may be formed between the transferable protective layer and the release layer. The release layer includes, for example, waxes, silicone wax, silicone resin, fluororesin, acrylic resin, polyvinyl alcohol resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acrylic vinyl ether resin, maleic anhydride resin, and It can be formed by applying and drying a coating solution containing at least one copolymer of these resin groups by a conventionally known method such as gravure coating or gravure reverse coating. Among the above-mentioned resins, the acrylic resin is preferably a resin such as acrylic acid or methacrylic acid or a resin copolymerized with other monomers, or a cellulose derivative resin. Adhesion with the support and separation from the protective layer are preferable. Excellent in moldability.
It is also possible to crosslink with various crosslinking agents, and ionizing radiation curable resins and ultraviolet curable resins can also be used.

  The release layer can be appropriately selected from those that transfer to the transfer medium during thermal transfer, those that remain on the support side, or those that coagulate and break down. However, the release layer is non-transferable, and can be transferred by thermal transfer. The release layer remains on the support side so that the interface between the release layer and the heat transferable protective layer becomes the surface of the protective layer after the thermal transfer, such as surface glossiness, transfer stability of the protective layer, etc. This is a preferred embodiment. The release layer can be formed by a conventionally known coating method, and the thickness is preferably 0.5 to 5 μm in a dry state.

[Adhesive layer]
As the uppermost layer of the transferable protective layer laminate, an adhesive layer can be provided on the outermost surface of the protective layer. As a result, the adhesion of the protective layer to the transfer target can be improved.
The adhesive layer can contain an ultraviolet absorber. As an ultraviolet absorber, the thing similar to what was used by the protective layer can be used, and its preferable range is also the same.

[Back layer]
In the heat-sensitive transfer ink sheet of the present invention, a back layer is preferably provided on the other side (back side) of the support surface on which the dye layer is coated, that is, on the side in contact with the thermal head or the like.
When heat is applied in a state where the back surface of the support of the heat-sensitive transfer ink sheet is in direct contact with a heating device such as a thermal head, thermal fusion tends to occur. Further, the friction between the two is large, and it is difficult to smoothly convey the thermal transfer ink sheet during printing.
The back layer is provided so that the heat-sensitive transfer ink sheet can withstand the thermal energy from the thermal head, and prevents thermal fusion and enables smooth running. In recent years, the thermal energy of thermal heads has increased with the increase in the speed of printers, and therefore the necessity has increased.
The back layer is formed by applying a binder, a lubricant, a release agent, a surfactant, inorganic particles, organic particles, a pigment and the like added thereto. In addition, an intermediate layer may be provided between the back layer and the support, and a layer made of inorganic fine particles and a water-soluble resin or an emulsifiable hydrophilic resin is disclosed.

As the binder, a known resin having high heat resistance can be used. Examples include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl acetoacetal Resin, vinyl chloride-vinyl acetate copolymer, vinyl resin such as polyvinylpyrrolidone, polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylic resin such as acrylonitrile-styrene copolymer, polyamide resin, polyimide resin, Polyamideimide resin, polyvinyltoluene resin, coumarone indene resin, polyester resin, polyurethane resin, polyether resin, polybuta Ene resin, polycarbonate resin, chlorinated polyolefin resin, fluorine resin, epoxy resin, phenol resin, silicone resin, mention may be made of a single or a mixture of natural or synthetic resins such as silicone-modified or fluorine-modified urethane.
In order to increase the heat resistance of the back layer, a technique for crosslinking a resin by irradiating ultraviolet rays or an electron beam is known. It is also possible to crosslink by heating using a crosslinking agent. At this time, a catalyst may be added. As the crosslinking agent, polyisocyanate and the like are known, and for this purpose, a resin having a hydroxyl group functional group is suitable. In JP-A-62-259889, a back layer is formed by adding a filler such as an alkali metal salt or alkaline earth salt of a phosphate ester and calcium carbonate to a reaction product of polyvinyl butyral and an isocyanate compound. Is disclosed. JP-A-6-99671 discloses that a polymer compound forming a heat-resistant slipping layer is reacted with a silicone compound having an amino group and an isocyanate compound having two or more isocyanate groups in one molecule. It is disclosed to obtain.

In order to fully exhibit the function, additives such as a lubricant, a plasticizer, a stabilizer, a filler, and a filler for removing head deposits may be blended in the back layer.
Lubricants include calcium fluoride, barium fluoride, fluoride such as fluoride fluoride, sulfides such as molybdenum disulfide, tungsten disulfide, iron sulfide, oxides such as lead oxide, alumina, molybdenum oxide, graphite, mica , Solid lubricants made of inorganic compounds such as boron nitride and clays (talc, acid whiteness, etc.), organic resins such as fluororesins and silicone resins, metal soaps such as silicone oil and metal stearate, polyethylene wax, paraffin Examples include various types of waxes such as waxes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and fluorosurfactants.
Phosphate ester surfactants such as alkyl phosphate monoesters and alkyl phosphate diester zinc salts are also used, but they have acid radicals, and when the amount of heat from the thermal head increases, the phosphate ester decomposes and the back side There is a problem that the pH of the layer is lowered and the corrosion wear of the thermal head becomes severe. For this, a method using a neutralized phosphate ester surfactant, a method using a neutralizing agent such as magnesium hydroxide, and the like are known.
Examples of other additives include higher fatty acid alcohols, organopolysiloxanes, organic carboxylic acids and derivatives thereof, and fine particles of inorganic compounds such as talc and silica.

  For the back layer, conventionally known methods such as gravure coating, roll coating, blade coating, and wire bar are applied to a coating solution in which a material obtained by adding an additive to a binder as exemplified above is dissolved or dispersed in a solvent. It is formed by coating with. A film thickness of 0.1 to 10 μm is preferable, and a film thickness of 0.5 to 5 μm is more preferable.

[Support]
The support for the heat-sensitive transfer ink sheet and transferable protective layer laminate of the present invention is not particularly limited, and any conventionally known one can be used as long as it has the required heat resistance and strength. .
Examples include polyamide, polyimide, and polyester film.
Although the thickness of a support body can be suitably changed according to material so that the intensity | strength, heat resistance, etc. may become suitable, Preferably it is 1-100 micrometers. More preferably, it is 2-50 micrometers, More preferably, the thing of 3-10 micrometers is used.
The heat-sensitive transfer sheet and the transferable protective layer laminate are preferably provided on the same support.

<Thermal transfer image-receiving sheet>
Next, a thermal transfer image receiving sheet (hereinafter also simply referred to as an image receiving sheet) will be described in detail.
The image-receiving sheet used in the present invention has at least one dye-receiving layer (hereinafter also simply referred to as a receiving layer) on a support, for example, a heat insulating layer between the support and the receiving layer. An intermediate layer such as a (porous layer), a gloss control layer, a white background adjustment layer, a charge adjustment layer, an adhesive layer, or a primer layer may be formed. An undercoat layer may be provided between these functional layers and the support. It is a preferred embodiment to have at least one heat insulating layer between the support and the receiving layer.
The receptor layer and these intermediate layers are preferably formed by simultaneous multilayer coating, and a plurality of intermediate layers can be provided as necessary.
A curl adjustment layer, a writing layer, and a charge adjustment layer may be 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]
The image-receiving sheet has at least one receiving layer containing a thermoplastic receiving polymer capable of receiving a dye. The receiving layer can contain an ultraviolet absorber, a release agent, a lubricant, an antioxidant, an antiseptic, a surfactant, and other additives.

(Thermoplastic resin)
In the present invention, a known thermoplastic resin can be used for the receiving layer.
Examples of the thermoplastic resin preferably include polycarbonate, polyester, polyurethane, polyvinyl chloride and a copolymer thereof, styrene-acrylonitrile copolymer, polycaprolactone, or a mixture thereof. Polyester, polyvinyl chloride and a mixture thereof More preferred are copolymers or mixtures thereof. The above polymers can be used alone or as a mixture thereof.

The polymer to be used can be coated on the support by dissolving it appropriately using an organic solvent (methyl ethyl ketone, ethyl acetate, toluene, xylene, etc.). Or it can also apply | coat on a support body in addition to a water-system coating liquid as polymer latex.
The polyester and polyvinyl chloride will be described in more detail below.

(Polyester polymer)
Polyester is obtained by polycondensation of a dicarboxylic acid component (including derivatives thereof) and a diol component (including derivatives thereof). The polyester polymer may contain an aromatic ring and / or an alicyclic ring. For alicyclic polyesters, the technique described in JP-A-5-238167 is effective in terms of dye uptake ability and image stability.

  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. It is preferable to use a polycondensed polyester polymer. If a material having a very low molecular weight is used, the elastic modulus of the receiving layer formed is low, the heat resistance is insufficient, and it may be difficult to ensure the releasability between the thermal transfer ink sheet and the image receiving sheet. . The molecular weight is preferably as large as possible from the viewpoint of increasing the elastic modulus, which may cause problems such as being unable to dissolve in the coating solution solvent during formation of the receiving layer, or may affect adhesion to the support after the receiving layer is applied and dried. There is no particular limitation as long as no adverse effects such as adverse effects occur, but the maximum is about 30000 or less, preferably about 25000 or less. In addition, as a synthesis method of the ester polymer, a conventionally known method can be used.

  As the saturated polyester, for example, Bironal MD1200, Bironal MD1220, Bironal MD1245, Bironal MD1250, Bironal MD1500, Bironal MD1930, Bironal MD1985 (all trade names, manufactured by Toyobo Co., Ltd.) and the like are used.

(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 monomer copolymerized with vinyl chloride is not particularly limited as long as it can be copolymerized with vinyl chloride, and vinyl acetate, acrylic acid ester, and methacrylic acid ester are particularly preferable. As the polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride are used. -An acrylic ester copolymer and a vinyl chloride-methacrylic ester copolymer are excellent. These copolymers are not necessarily limited to the case of being a copolymer of only a vinyl chloride component and the above-mentioned preferred monomer (vinyl acetate, acrylate ester, or methacrylic ester) component, and a range that does not hinder the object of the present invention. It may contain a vinyl alcohol component, a maleic acid component, and the like. Other monomer components constituting such a copolymer comprising vinyl chloride and the above preferred monomers as main monomers include vinyl alcohol derivatives such as vinyl alcohol and vinyl propionate, acrylic acid and methacrylic acid. And their acrylic 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, Examples thereof include vinyl ether derivatives such as 2-ethylhexyl vinyl ether, acrylonitrile, methacrylonitrile, styrene, and vinyl acetate. The component ratio of the vinyl chloride incorporated in the copolymer and the above preferred monomer 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 the above-mentioned vinyl chloride and the above-mentioned preferable monomers are 10% by mass or less.

Examples of such vinyl chloride-vinyl acetate copolymers include Viniblanc 240, Vinibrand 601, Vinibrand 602, Vinibrand 380, Vinibrand 386, Vinibrand 410, Vinybrand 550 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), etc. Is mentioned.
Examples of the vinyl chloride-acrylic acid ester copolymer include VINYBRAN 270, VINYBRAN 276, VINYBRAN 277, VINYBRAN 609, VINYBRAN 680, VINYBRAN 690, VINYBRAN 900 (all are trade names, manufactured by Nissin Chemical Industry Co., Ltd.) and the like. It is done.

(Polymer latex)
A polymer latex can be preferably used for the receiving layer. 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 receptor layer is preferably one in which a hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably 5 to 1000 nm.

  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 130 ° C., more preferably 0 ° C. to 120 ° C., and further preferably 10 ° C. to 100 ° C.

  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 are miscible with water such as methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, and oxyethyl phenyl ether. These organic solvents can be used.

  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, and natural resin polymers and copolymers, synthetic resin polymers and copolymers, and other media forming films such as gelatins, polyvinyl alcohols, Examples include hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrates, and polyvinyl pyrrolidones.

(binder)
The binder used in the present invention preferably has a glass transition temperature (Tg) in the range of −30 ° C. to 90 ° C., more preferably in the range of −10 ° C. to 85 ° C. in view of processing brittleness and image storage stability. Preferably it is the range of 0 degreeC-70 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.

(Release agent)
In the present invention, a release agent may be used 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 the release agent include solid waxes such as polyethylene wax and amide wax, silicone oils, phosphate ester compounds, fluorine surfactants, silicone surfactants, and other release agents known in the art. Fluorine compounds such as fluorine-based surfactants, silicone-based compounds such as silicone surfactants, silicone oils and / or cured products thereof are preferably 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 not to the receptor layer but to the release layer formed on the receptor layer. Also in this case, the above-described receiving layer may be used, and silicone may be added to the receiving layer. 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 of silicone alone, or may be used as a binder mixed with a compatible resin. The release layer has a thickness of 0.001 to 1 g / m ² .

[Insulation layer]
(Hollow polymer)
In the image receiving sheet used in the present invention, the heat insulating layer preferably contains a hollow polymer and a water-soluble polymer.
The hollow polymer in the present invention is a polymer particle having a void inside the particle. For example, [1] a dispersion medium such as water is contained in the partition wall formed of polystyrene, acrylic resin, styrene-acrylic resin, etc., and after coating and drying, the dispersion medium in the particles evaporates outside the particles and the inside of the particles A non-foamed hollow polymer particle in which is hollow, [2] a low boiling point liquid such as butane or pentane, polyvinylidene chloride, polyacrylonitrile, polyacrylic acid, polyacrylic ester, or a mixture or polymer thereof A foamed microballoon which is covered with a resin and is coated and then expands when the low-boiling liquid inside the particles expands by heating. [3] The above-mentioned [2] is heated and foamed in advance to form a hollow Examples thereof include microballoons made of polymers.

The particle size of these hollow polymers is preferably from 0.1 to 20 μm, more preferably from 0.1 to 5.0 μm, further preferably from 0.2 to 3.0 μm, particularly preferably from 0.3 to 1.0 μm.
The void ratio of the hollow polymer is preferably 20 to 70%, more preferably 20 to 50%. The void ratio of the hollow polymer indicates the ratio of the volume of the void portion to the particle volume.

  The glass transition temperature (Tg) of the hollow polymer is preferably 70 ° C. or higher, and more preferably 90 ° 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.

(Water-soluble polymer)
A water-soluble polymer can be used as the binder of the heat insulating layer. The water-soluble polymer that can be used for the heat insulating layer is preferably a polymer used in combination with a polymer latex.

  In the present invention, the water-soluble polymer used as the binder of the heat insulating layer is preferably polyvinyl alcohols or gelatin, and most preferably gelatin.

  Further, the water-soluble polymer contained in the heat insulating layer may be cross-linked with a hardener in order to adjust cushioning properties and film strength. In the case of crosslinking with a dura, as a hardening agent, H-1,4,6,8,14 on page 17 of JP-A-1-214845, column 13 to U.S. Pat. No. 4,618,573. 23 compounds (H-1 to 54) represented by formulas (VII) to (XII), compounds (H-1 to 76) represented by formula (6) on page 8, lower right of JP-A-2-214852, In particular, H-14 and the compounds described in claim 1 of US Pat. No. 3,325,287 are preferably used.

[Support]
The support for the heat-sensitive transfer image-receiving sheet is not particularly limited, and known coated paper, laminated paper, and synthetic paper can be used.
[Curl adjustment layer, writing layer, charge adjustment layer]
In the heat-sensitive transfer image-receiving sheet used in the present invention, a curl adjusting layer, a writing layer, and a charge adjusting layer can be provided on the other surface (back surface) of the support on which the receiving layer is coated, if necessary.

<Image forming method>
In the image forming method of the present invention, an image is formed by applying heat energy corresponding to an image signal from a thermal head by superimposing the receiving layer of the thermal transfer image receiving sheet and the thermal transfer layer of the thermal transfer sheet so as to contact each other. To do.
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 or less. 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. to 450 ° C., more preferably 200 ° C. to 450 ° C. Furthermore, 350 to 450 degreeC is 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 heat-sensitive transfer image-receiving sheet of the present invention can be applied to various uses such as a sheet- or roll-shaped heat-sensitive transfer image-receiving sheet, cards, and transmission-type manuscript preparation sheets capable of thermal transfer recording by appropriately selecting a support. You can also

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the present invention is not limited to these. In Examples, “part” or “%” is based on mass unless otherwise specified.

Synthesis Example 1 (Preparation example of N-phenylmaleimide / isobutene copolymer)
A stainless steel autoclave was charged with 323 parts by mass of N-phenylmaleimide, 1.5 parts by mass of tert-butyl peroxypivalate and 606 parts by mass of methyl ethyl ketone, purged several times with nitrogen, and then charged with 105 parts of liquefied isobutene at 60 ° C. Polymerization was performed for 8 hours. The solution after completion of the reaction was cooled to room temperature, gradually added to methanol for reprecipitation treatment, and then filtered and dried to obtain a copolymer.

^The copolymer produced by ¹ H-NMR measurement is an N-phenylmaleimide residue unit: isobutene residue unit = 60/40 (molar ratio) N-phenylmaleimide / isobutene copolymer (hereinafter referred to as copolymer A ( 1).) Was confirmed. Moreover, the mass mean molecular weight was 140,000 and the glass transition temperature was 220 degreeC.

Synthesis Example 2 (Preparation example of N- (2-methylphenyl) maleimide / isobutene copolymer)
A stainless steel autoclave was charged with 335 parts by weight of N- (2-methylphenyl) maleimide, 1.9 parts by weight of tert-butyl peroxypivalate and 610 parts by weight of methyl ethyl ketone, purged several times with nitrogen, and then 111 parts by weight of liquefied isobutene. Polymerization was carried out at 60 ° C. for 8 hours. The solution after completion of the reaction was cooled to room temperature, gradually added to methanol for reprecipitation treatment, and then filtered and dried to obtain a copolymer.

^The copolymer produced by ¹ H-NMR measurement is N- (2-methylphenyl) maleimide unit residue: isobutene unit residue = 59: 41 (molar ratio) of N- (2-methylphenyl) maleimide / isobutene copolymer. It was confirmed that it was a polymer (hereinafter referred to as copolymer A (2)). Moreover, the mass mean molecular weight was 150,000 and the glass transition temperature was 215 degreeC.

Synthesis Example 3 (Preparation example of N-phenylmaleimide / isobutene copolymer)
A stainless steel autoclave was charged with 300 parts by weight of N-phenylmaleimide, 1.0 part by weight of tert-butyl peroxypivalate and 660 parts by weight of methyl ethyl ketone, purged several times with nitrogen, and then charged with 112 parts by weight of liquefied isobutene at 60 ° C. For 8 hours. The solution after completion of the reaction was cooled to room temperature, gradually added to methanol for reprecipitation treatment, and then filtered and dried to obtain a copolymer.

^The copolymer produced by ¹ H-NMR measurement was N-phenylmaleimide residue unit: isobutene residue unit = 57/43 (molar ratio) N-phenylmaleimide / isobutene copolymer (hereinafter referred to as copolymer A ( 3).) Was confirmed. Moreover, the mass mean molecular weight was 170,000 and the glass transition temperature was 209 degreeC.

Synthesis Example 4 (Preparation example of N-phenylmaleimide / isobutene copolymer)
A stainless steel autoclave was charged with 43 parts by weight of N-phenylmaleimide, 0.2 parts by weight of tert-butyl peroxypivalate and 750 parts by weight of methyl ethyl ketone, purged several times with nitrogen, and then charged with 140 parts by weight of liquefied isobutene at 60 ° C. For 8 hours. The solution after completion of the reaction was cooled to room temperature, gradually added to methanol for reprecipitation treatment, and then filtered and dried to obtain a copolymer.

^The copolymer produced by ¹ H-NMR measurement was N-phenylmaleimide residue unit: isobutene residue unit = 50/50 (molar ratio) N-phenylmaleimide / isobutene copolymer (hereinafter referred to as copolymer A ( 4).) Was confirmed. Moreover, the mass mean molecular weight was 190,000 and the glass transition temperature was 192 degreeC.

Synthesis Example 5 (Preparation example of N-phenylmaleimide / isobutene copolymer)
A stainless steel autoclave was charged with 369 parts by weight of N-phenylmaleimide, 2.2 parts by weight of tert-butyl peroxypivalate and 606 parts by weight of methyl ethyl ketone, purged several times with nitrogen, and then charged with 72 parts of liquefied isobutene at 60 ° C. Polymerization was performed for 8 hours. The solution after completion of the reaction was cooled to room temperature, gradually added to methanol for reprecipitation treatment, and then filtered and dried to obtain a copolymer.

^The copolymer produced by ¹ H-NMR measurement was N-phenylmaleimide residue unit: isobutene residue unit = 66/34 (molar ratio) N-phenylmaleimide / isobutene copolymer (hereinafter referred to as copolymer A ( 5).) Was confirmed. Moreover, the mass mean molecular weight was 82,000 and the glass transition temperature was 235 degreeC.

Synthesis Example 6 (Preparation example of acrylonitrile-styrene copolymer)
A stainless steel autoclave is charged with 44 parts by weight of acrylonitrile, 32 parts by weight of styrene, 24 parts by weight of ethylbenzene, 0.3 part by weight of α-methylstyrene dimer and 0.01 part by weight of tert-butylperoxyisopropyl carbonate, and purged several times with nitrogen. Then, polymerization was carried out at 140 ° C. for 1.7 hours. Subsequently, the obtained polymer solution was extracted from the autoclave and transferred to a container equipped with a deaeration device (hereinafter referred to as container-1), and then the container-1 was heated to 160 ° C. and degassed at a vacuum degree of 8000 Pa. did. Further, after the polymer solution was transferred from the container-1 to another container (hereinafter referred to as container-2) equipped with a deaeration device, the container-2 was heated to 260 ° C. and degassed at a vacuum degree of 4000 Pa. Then, the copolymer was obtained by extracting from the container-2.

^The copolymer produced by ¹ H-NMR measurement is an acrylonitrile residue unit: styrene residue unit = 46/54 (mass ratio) acrylonitrile-styrene copolymer (hereinafter referred to as copolymer B (1)). It was confirmed that. Moreover, the mass mean molecular weight was 120,000 and the glass transition temperature was 113 degreeC.

Synthesis Example 7 (Preparation example of acrylonitrile-styrene copolymer)
A stainless steel autoclave is charged with 48 parts by weight of acrylonitrile, 33 parts by weight of styrene, 24 parts by weight of ethylbenzene, 0.3 part by weight of α-methylstyrene dimer and 0.01 part by weight of tert-butylperoxyisopropyl carbonate, and purged several times with nitrogen. Thereafter, a copolymer was obtained in the same manner as in Synthesis Example 6 except that the polymerization was carried out at 148 ° C. for 0.9 hours.

^The copolymer produced by ¹ H-NMR measurement was an acrylonitrile-styrene copolymer (hereinafter referred to as copolymer B (2)) having an acrylonitrile residue unit: styrene residue unit = 51/49 (mass ratio). It was confirmed that. Moreover, the mass mean molecular weight was 120,000 and the glass transition temperature was 116 degreeC.

Synthesis Example 8 (Preparation example of N-methylmaleimide / isobutene copolymer)
A stainless steel autoclave is filled with 100 parts by mass of a maleic anhydride / isobutene copolymer (trade name Isoban 10 manufactured by Kuraray Co., Ltd.) and 500 parts by mass of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a solvent. The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Next, after introducing 40 parts by mass of methylamine at room temperature, the mixture was heated to 80 ° C. and stirred for 1 hour to carry out amidation reaction of maleic anhydride units. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour to carry out an imidization reaction, the mixture was cooled to room temperature and reprecipitated using isopropanol to obtain a copolymer.

The copolymer produced by elemental analysis, infrared absorption spectrum measurement and ¹³ C-NMR measurement is an N-methylmaleimide / isobutene copolymer of N-methylmaleimide residue: isobutene residue = 50/50 (molar ratio) ( Hereinafter, it was described as copolymer A (6).). Moreover, the mass mean molecular weight was 180,000 and the glass transition temperature was 159 degreeC.

  Moreover, the following copolymer was obtained. Acrylonitrile-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name Stylac 727, mass average molecular weight = 130,000, acrylonitrile residue unit: styrene residue unit (mass ratio) = 38: 62) (Referred to as polymer B (3)). Acrylonitrile-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Stylac 789, mass average molecular weight = 14,000, acrylonitrile residue unit: styrene residue unit (mass ratio) = 28: 72) (hereinafter referred to as copolymer) B (4)), polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name ESREC KS-1) (hereinafter referred to as copolymer C (1)).

<Production of Example 101>

(Preparation of coating solution)
Next, a back layer coating layer, yellow, magenta and cyan dye coating solutions containing the polyvinyl alcohol resin AP-1, a releasable coating solution, a protective layer coating solution and an adhesive layer coating solution Produced. Each composition is shown below.

Back layer coating solution Acrylic polyol resin 26.0 parts by mass (Acridic A-801, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
Zinc stearate 0.43 parts by mass (SZ-2000, trade name, manufactured by Sakai Chemical Industry Co., Ltd.)
Phosphate ester 1.27 parts by mass (Pricesurf A217E, trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Isocyanate (50% solution) 8.0 parts by mass (Bernock D-800, trade name, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl ethyl ketone / toluene (mass ratio 2/1) 64 parts by mass

Yellow dye layer coating solution Dye compound (Y1-1) 3.9 parts by mass Dye compound (Y2-1) 3.9 parts by mass Copolymer A (1) 3.28 parts by mass Copolymer B (3) 4 .92 parts by mass Release agent 0.05 parts by mass (X-22-3000T, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Release agent 0.03 parts by mass (TSF4701, trade name, Momentive Performance
(Materials Japan GK)
Matting agent 0.15 parts by mass (Flosen UF, trade name, manufactured by Sumitomo Seiko Co., Ltd.)
84 parts by mass of methyl ethyl ketone / toluene (mass ratio 2/1)

Magenta dye layer coating solution Dye compound (M1-1) 0.1 part by weight Dye compound (M2-1) 0.7 part by weight Dye compound (M3-1) 7.0 part by weight Copolymer A (1) 3 .28 parts by mass Copolymer B (3) 4.92 parts by mass Release agent 0.05 part by mass (X-22-3000T, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Release agent 0.03 parts by mass (TSF4701, trade name, Momentive Performance
(Materials Japan GK)
Matting agent 0.15 parts by mass (Flosen UF, trade name, manufactured by Sumitomo Seiko Co., Ltd.)
84 parts by mass of methyl ethyl ketone / toluene (mass ratio 2/1)

Cyan dye layer coating solution Dye compound (C1-1) 1.2 parts by mass Dye compound (C1-3) 6.6 parts by mass Copolymer A (1) 3.28 parts by mass Copolymer B (3) 4 .92 parts by mass Release agent 0.05 parts by mass (X-22-3000T, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Release agent 0.03 parts by mass (TSF4701, trade name, Momentive Performance
(Materials Japan GK)
Matting agent 0.15 parts by mass (Flosen UF, trade name, manufactured by Sumitomo Seiko Co., Ltd.)
84 parts by mass of methyl ethyl ketone / toluene (mass ratio 2/1)

Release layer coating solution Modified cellulose resin 5.0 parts by mass (L-30, trade name, Daicel Chemical)
Methyl ethyl ketone 95.0 parts by mass Protective layer coating solution Acrylic resin 30 parts by mass (Dianal BR-100, trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
Isopropanol 70 parts by mass Adhesive layer coating solution Acrylic resin 25 parts by mass (Dianal BR-77, trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
1 part by weight of the following UV absorbent UV-1 2 parts by weight of the following UV absorbent UV-2 1 part by weight of the following UV absorbent UV-3 1 part by weight of the following UV absorbent UV-4 PMMA fine particles (polymethyl methacrylate fine particles) 0. 4 parts by mass Methyl ethyl ketone / toluene (mass ratio 2/1) 70 parts by mass

(Preparation of thermal transfer ink sheet)
On the surface where the easy adhesion treatment of a 6.0 μm thick polyester film (Diafoil K200E-6F, trade name, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) that has been subjected to easy adhesion treatment on one side as a support, The back layer coating solution was applied so that the solid content coating amount after drying was 1 g / m ² . After drying, it was cured by heat treatment at 60 ° C.
A dye layer was prepared by applying the yellow, magenta, and cyan dye coating liquids to the easy-adhesion treated surface of the polyester film after thermosetting. The solid content coating amount of each dye layer was 0.8 g / m ² .
Further, by applying the release layer coating solution, the protective layer coating solution and the adhesive layer coating solution having the above composition on the same side as the dye layer to form a transferable protective layer laminate, yellow, magenta A thermal transfer sheet was prepared by coating each of the cyan thermal transfer layers and the protective layer in a surface sequential manner. In addition, the transferable protective layer laminate is formed by applying a release layer coating solution and drying it, then applying a protective layer coating solution thereon, drying, and then further applying an adhesive layer coating thereon. The liquid was applied. The coating amount of the releasing layer 0.3 g / m ² when dry film, the protective layer 0.5 g / m ^2, and an adhesive layer 2.2 g / m ^2.

<Production of Examples 102 to 107>
Examples 102 to 107 were prepared in the same manner as in Example 101 except that the copolymer A (1) and the copolymer B (3) were changed to the copolymers described in Table 22 described later. .

<Production of Comparative Examples 201 to 208>
Comparative Examples 201-208 were prepared in the same manner as in Example 101 except that the copolymer A (1) and the copolymer B (3) were changed to the copolymers described in Table 22 described later. .

(Preparation of thermal transfer image-receiving sheet)
The paper support surface laminated on both sides with polyethylene was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. 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 FIG. 9 in US Pat. No. 2,761,791. The simultaneous multilayer coating was carried out by the method exemplified in 1. Each dry coating weight of the subbing layer: 6.7g / m ^2, the heat insulating layer: 8.7g / m ^2, Lower receptor layer: 2.6g / m ^2, Upper receptor layer: 2.7 g / m ² The coating was performed so that Moreover, the following composition represents the mass part as solid content.

Receptive layer upper layer 22.0 parts by mass of vinyl chloride latex (Viniblanc 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
2.4 parts by mass of vinyl chloride latex (Viniblanc 276, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Gelatin (10% aqueous solution) 2.0 parts by mass The following ester wax EW-1 2.0 parts by mass The following surfactant F-1 0.07 parts by mass The following surfactant F-2 0.36 parts by mass Receiving layer lower layer 12.0 parts by mass of vinyl chloride latex (Viniblanc 690, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
12.0 parts by mass of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Gelatin (10% aqueous solution) 10.0 parts by mass The following surfactant F-1 0.04 parts by mass Thermal insulation layer Hollow polymer particle latex 60.0 parts by mass (MH5055, trade name, manufactured by Nippon Zeon Co., Ltd.)
Gelatin (10% aqueous solution) 30.0 parts by mass Undercoat layer 6.7 parts by mass of polyvinyl alcohol (Poval PVA205, trade name, manufactured by Kuraray Co., Ltd.)
60.0 parts by mass of styrene butadiene rubber latex (SN-307, trade name, manufactured by Nippon A & L Co., Ltd.)
0.03 part by mass of the following surfactant F-1

[Test example]
(Image formation)
152 mm by thermal transfer printer A (ASK-2000 manufactured by Fuji Film Co., Ltd.) and thermal transfer printer B (CW-01 manufactured by Citizen Co., Ltd.) using the above comparative example and the thermal transfer sheet and thermal transfer image-receiving sheet of the present invention. A × 102 mm size image was output. The line speed of the thermal transfer printer A was 0.73 msec / line, and the maximum temperature reached by the thermal printer head was 410 ° C. The line speed of the thermal transfer printer B was 1.1 msec / line, and the maximum temperature reached by the thermal printer head was 280 ° C. These were printed in an environment of 25 ° C. and 55% relative humidity.
Ten continuous images of yellow solid were output as images, and the optical density of each was measured, and the average value obtained by measuring 10 sheets each was obtained. Next, 10 solid black images were output in succession, the optical density of each was measured, and the average value obtained by measuring 10 images was obtained. For the measurement of the optical density, the reflection density was measured with Xrite 310 manufactured by Xrite, and the measured value of the yellow (Y) density in each sample was used.

(Relative transfer density evaluation)
The Visual density of the black image obtained under the above conditions was measured with a Photographic Densitometer (manufactured by X-Rite Incorporated). Table 22 below shows relative values when the transfer density of Comparative Example 208 is 100.

(Dye preservation stability evaluation)
After the thermal transfer ink sheet was stored at 55 ° C. and 65% humidity for 6 days, the relative transfer density was evaluated in the same manner as described above. When the dye storage stability is insufficient, the transfer density decreases. Table 22 below shows relative values when the dye preservability of Comparative Example 208 is taken as 100.
In Table 22, the relative transfer density is 0.73 msec / line for the relative transfer density, and the result is shown for the thermal transfer printer A capable of high-speed transfer recording, but the same tendency is shown for the thermal transfer printer B. It was.

As is apparent from Table 22 above, Comparative Examples 201-204 cannot achieve both good transferability and dye storage stability during high-speed transfer recording. In Examples 101 to 107 of the present invention, good transferability was obtained even during high-speed transfer recording, and dye storage stability was sufficient. Thus, by using the copolymer of the present invention, it was possible to obtain a thermal transfer ink sheet having good transferability even during high-speed transfer recording and good dye storage stability.
In addition, the same tendency was shown even if the line speed of the printer was 1.4 msec / line and the thermal head temperature was adjusted so that the amount of heat applied during Dmax printing was the same.

Claims (8)

It has a dye layer in which a heat transferable dye is contained in a resin binder on a support, and the resin binder of the dye layer comprises an α-olefin residue unit represented by the following formula (i) and A thermal transfer ink sheet comprising a copolymer (a) having an N-phenyl-substituted maleimide residue unit represented by formula (ii) in a molar ratio of 49:51 to 35:65.

(Here, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

(Wherein R ⁴ and R ⁵ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently Represents a hydrogen atom, a halogen atom, a carboxyl group or a salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, a cyano group, a nitro group, or a linear or branched alkyl group having 1 to 8 carbon atoms.)   The resin binder of the dye layer further contains an acrylonitrile-styrene copolymer (b) having an acrylonitrile residue unit and a styrene residue unit in a mass ratio of 36:64 to 50:50. Item 2. The thermal transfer ink sheet according to Item 1. The copolymer (a) and the copolymer (b) each have a mass average molecular weight in terms of standard polystyrene of 5 × 10 ^{3 to} 5 × 10 ⁶ . Thermal transfer ink sheet.   The resin binder of the said dye layer consists of said copolymer (a) 20-85 mass% and said acrylonitrile-styrene copolymer (b) 80-15 mass%, Any of Claims 1-3 characterized by the above-mentioned. The thermal transfer ink sheet according to claim 1.   The copolymer (a) is an N-phenylmaleimide-isobutene copolymer and / or an N- (2-methylphenyl) maleimide-isobutene copolymer. The thermal transfer ink sheet according to item.   An ink cartridge filled with the thermal transfer ink sheet according to any one of claims 1 to 5.   An image is formed using the thermal transfer ink sheet according to any one of claims 1 to 5 on a thermal transfer image receiving sheet having an ink receiving layer containing a polymer latex on a support. Thermal transfer recording method.   A coating composition for a dye layer of a thermal transfer ink sheet, comprising a binder containing the copolymer according to any one of claims 1 to 5 and a heat transferable dye.