JP4957562B2 - Thermal transfer recording medium - Google Patents

Description

  The present invention relates to a thermal transfer recording medium used in a thermal transfer system, and more particularly, to a thermal transfer recording medium having good printing characteristics and particularly excellent density development in a sublimation thermal transfer system.

  Conventionally, various thermal transfer recording methods are known. Among them, thermal transfer having a dye layer in which a dye for sublimation transfer is used as a recording material and this is supported on a base material such as a polyester film with an appropriate binder resin. A method for forming various full-color images by thermally transferring a sublimation dye from a sheet onto a transfer material that can be dyed with a sublimation dye, for example, a thermal transfer image-receiving sheet in which a dye-receiving layer is formed on paper or plastic film is proposed. ing.

  In this sublimation type thermal transfer recording method, a thermal head provided in a sublimation type thermal transfer printer is used as a heating means for heating the sublimation dye, and a large number of heating amounts of three colors or four colors can be obtained by heating with the thermal head. The adjusted color dots are transferred to the receiving layer of the thermal transfer image receiving sheet, and the full color image of the original is reproduced with the multicolored color dots. Since the color material used is a dye, the image formed in this way is very clear and excellent in transparency. It is possible to form a high-quality image similar to an image obtained by gravure printing and comparable to a full-color photographic image.

  In such a sublimation type thermal transfer recording method, as the printing speed of the thermal transfer printer increases, there is a problem that a sufficient print density cannot be obtained with the conventional thermal transfer sheet. Furthermore, in recent years, there has been a demand for higher density and clearer prints of images obtained by thermal transfer, and an image is formed by receiving a thermal transfer sheet and sublimation dye transferred from the thermal transfer sheet. Many attempts have been made to improve thermal transfer image receiving sheets.

  For example, an attempt is made to increase the printing density by increasing the ratio of dye to resin (dye / resin) in the dye layer of the thermal transfer sheet. However, in this method, when the thermal transfer sheet is wound and stored, the dye layer formed on the surface of the thermal transfer sheet and the heat-resistant slip layer formed on the back surface overlap, and during the winding storage, the back surface of the thermal transfer sheet The dye migrates to the heat-resistant slipping layer on the side. When the thermal transfer sheet is rewound, the dye transferred to the heat resistant slipping layer is re-transferred (kicked back) to a dye layer of another color. When printing with a contaminated dye layer in this way, the so-called background stain (ground fogging), which causes the dye to transfer to the thermal transfer image-receiving sheet even though it has a hue different from the specified color or is not heated. Will occur. Further, when the ratio of the dye and the resin (dye / resin) in the dye layer of the thermal transfer sheet is increased, there arises a problem that the crystallization of the dye occurs in a high temperature and humidity environment.

  In order to improve such a background fog and improve the printing density, Patent Document 1 below describes a thermal transfer sheet in which a primer layer made of polyvinylpyrrolidone resin is provided between a dye layer and a support. ing. In such a thermal transfer sheet, by forming the primer layer with a hydrophilic polyvinyl pyrrolidone resin, when the dye layer is heated by a thermal head, it is possible to prevent the oily dye from moving to the primer layer side, and thermal transfer image receiving The dye transferred to the sheet side does not decrease, and a good printing density can be obtained.

  However, in this thermal transfer sheet, since the primer layer exhibits hydrophilicity, the adhesion between the dye layer containing the dye and the primer layer is poor, and the holding power of the dye layer on the support is not sufficient. Abnormal transfer that transfers to the thermal transfer image-receiving sheet may occur, or when the thermal transfer image-receiving sheet is used in a high or low temperature environment or a low releasability, the thermal transfer sheet and the thermal transfer image-receiving sheet may be fused. These problems occur remarkably in high-speed printing.

  In addition, in the thermal transfer sheet described in Patent Document 2 below, attempts have been made to improve transfer sensitivity by including a colloidal inorganic pigment in the primer layer, but the smoothness of the thermal transfer sheet is impaired, Image unevenness and gloss unevenness occur.

JP 2005-271463 A JP 2006-150956 A

  Therefore, the present invention has high print density expression, can suppress fusion with the thermal transfer image-receiving sheet and abnormal transfer that is transferred together with the dye layer, and in particular, high-speed print has high print density expression and thermal transfer. It is an object of the present invention to provide a thermal transfer recording medium capable of suppressing fusion and abnormal transfer with an image receiving sheet.

  In the thermal transfer recording medium according to the present invention that achieves the above-mentioned object, a primer layer is formed on one surface of a substrate, and at least one or two or more dye layers are formed on the primer layer. A heat resistant slipping layer is formed on the surface, the primer layer contains a fluorosurfactant, and the dye layer contains a dye selected from the following general formula (1): Features.

（式中、Ｒ１及びＲ２は、置換又は非置換のアルキル基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、又は置換又は非置換のアリール基を表わし、Ｒ３、Ｒ４、Ｒ５およびＲ６は、水素原子、ハロゲン原子、シアノ基、水酸基、置換又は非置換のアルキル基、置換又は非置換のアルコキシ基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、置換又は非置換のアリール基、置換又は非置換のアシル基、置換又は非置換のアシルアミノ基、又は置換又は非置換のスルホニルアミノ基を表わし、Ｒ７は、水素原子を表し、Ｒ８は、水素原子又は置換又は非置換のアルキル基を表わし、Ｒ９は、水素原子又はハロゲン原子を表わし、Ｒ１０は、置換又は非置換のアルキル基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、置換又は非置換のアリール基、又は置換又は非置換のアルコキシ基を表わす。）

(Wherein R1 and R2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; R3, R4, R5 And R6 represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or Represents an unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acylamino group, or a substituted or unsubstituted sulfonylamino group; R7 represents a hydrogen atom; and R8 represents a hydrogen atom or a substituted or unsubstituted sulfonylamino group. Represents an unsubstituted alkyl group, R9 represents a hydrogen atom or a halogen atom, and R10 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexane. Alkyl represents group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group.)

  In the present invention, a fluorine-based dye layer containing a dye selected from the general formula (1) is formed on one surface of a substrate via a primer layer containing a fluorine-based surfactant. When the surfactant is transferred to the dye layer and the dye is not transferred, the crystallization of the dye is suppressed, and during the thermal transfer of the dye, the dye is prevented from diffusing to the substrate side, and the dye transferred to the thermal transfer image receiving sheet side is added. Concentration development is high without decreasing, and the dye layer is sufficiently retained by the primer layer, and the fluorosurfactant in the dye layer improves the peelability between the dye layer and the thermal transfer image-receiving sheet, thereby enabling thermal transfer. It is possible to suppress occurrence of fusion and abnormal transfer with the image receiving sheet. In the present invention, even if high-speed printing is performed, density development is high, and fusion and abnormal transfer with a thermal transfer image receiving sheet can be suppressed.

  Hereinafter, a thermal transfer recording medium to which the present invention is applied will be described in detail with reference to the drawings.

  As shown in FIG. 1, the thermal transfer recording medium 1 is provided with a primer layer 3 on one surface 2 a of a substrate 2 for adjusting the coating properties and adhesiveness of the dye layers 4Y, 4M, and 4C. On the top, there are three dye layers 4Y, 4M, and 4C of yellow, magenta, and cyan containing dyes, and a protective layer 6 that protects the formed image through the non-transferable release layer 5. They are arranged side by side. The thermal transfer recording medium 1 includes a cyan dye layer 4C, a yellow dye layer 4Y and a magenta dye layer 4M are provided as necessary, and the release layer 5 and the protective layer 6 are also provided as necessary. Try to provide it. On the other surface 2 b of the substrate 2, a heat-resistant slipping layer 7 that improves the running property of the thermal transfer recording medium 1 is formed.

  The thermal transfer recording medium 1 is attached to a thermal transfer printer device, and the dye layers 4Y, 4M, and 4C are heated from the other surface 2b of the substrate 2 by heating means such as a thermal head, and the prints conveyed into the thermal transfer printer device. Yellow, magenta, and cyan dyes are thermally transferred to a thermal transfer image-receiving sheet such as paper to form a color image, and then the protective layer 6 is heated and the protective layer 6 is in contact with the release layer 5. And the protective layer 6 is thermally transferred onto the formed color image to protect the color image.

  The base material 2 of the thermal transfer recording medium 1 is not particularly limited, such as plastic film, paper, synthetic paper, cellophane, etc., and can withstand the heating temperature of heating means such as a thermal head, and heat transfer is fast, and the dye layer 4Y 4M, 4C and the protective layer 6 are preferably made of a thin film having no thickness unevenness so that heating can be performed uniformly.

  Examples of the substrate 2 include polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate, Mention may be made of unstretched or stretched films such as fluororesin, polymethyl methacrylate, polybutene 1, polyetheretherketone, polysulfone, polyethersulfone, polyphenylene sulfide. Among these, the base material 2 is preferably a plastic film of polyethylene terephthalate, polyethylene naphthalate, or polyetheretherketone, which has excellent heat resistance and can be produced with little unevenness in thickness. The plastic film has a primer coat, a corona discharge treatment, etc. in order to strengthen the adhesion of the dye layers 4Y, 4M, 4C, the protective layer 6 and the heat resistant slipping layer 7 to the one surface 2a and the other surface 2b. In addition, it is preferable to perform surface treatment such as antistatic in order to prevent adhesion of foreign matter and to stabilize the traveling of the sheet.

The base material 2 preferably has a thickness of 3.5 to 12 μm, particularly preferably 4.0 to 6.0 μm. By setting the thickness of the substrate 2 in the range of 3.5 to 12 μm, heat resistance of the thermal transfer recording medium 1 can be obtained, and in order to thermally transfer the dye and the protective layer 6, There is no step when superimposed, and the color tone reproducibility does not deteriorate. The base material 2 preferably has a breaking strength of 10 to 40 kg / mm ² both vertically and horizontally, and a break elongation of 50 to 150% both vertically and horizontally (both according to JIS C2318). By setting the breaking strength to 10 to 40 kg / mm ² and the breaking elongation to 50 to 150%, it is preferable that the film does not stretch or break during winding or printing.

  The primer layer 3 is applied between the base material 2 and the dye layers 4Y, 4M, 4C and the release layer 5, and the coatability and adhesion of the dye layers 4Y, 4M, 4C, the release layer 5 and the protective layer 6 are as follows. Formed for the purpose of adjusting. The primer layer 3 is formed of at least a resin and a specific fluorosurfactant.

  The resin forming the primer layer 3 preferably contains at least one of water-soluble or water-dispersible polyester resin, polyacrylic resin, and polyurethane resin.

  As the water-soluble or water-dispersible polyester resin, known polyesters or polyester resins based thereon can be used as described in JP-B-47-40873 and JP-A-58-78761. For example, among dicarboxylic acid components in polyesters, examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,5-naphthalenedicarboxylic acid and ester-forming derivatives thereof, and aliphatic dicarboxylic acid. Examples include adipic acid, azelaic acid, sebacic acid and ester-forming derivatives thereof, and examples of oxymonocarboxylic acid include oxybenzoic acid and ester-forming derivatives thereof.

  Furthermore, as the glycol component of the polyester, aliphatic, alicyclic, aromatic diol and the like can be used. Examples thereof include ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol. And p-xylenediol, and examples of poly (oxyalkylene) glycols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The polyester having a sulfonate group is obtained by substituting a sulfonate group for the above-described polyester forming component. Examples of the dicarboxylic acid component for producing such a polyester include sulfoisophthalic acid, sulfoterephthalic acid, 4- Examples thereof include metal salts such as sulfonaphthalene-2,7-dicarboxylic acid and ester-forming derivatives thereof. As examples of the metal in the metal salt, lithium, sodium, potassium, magnesium and the like are preferable. Of these, 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid are particularly preferable.

  The amount of the aromatic dicarboxylic acid in the dicarboxylic acid component of the polyester resin is preferably in the range of 50 mol% to 100 mol%. This is for increasing the softening point of the polyester resin and improving the fixing property. The sulfonate group in the polyester-based resin needs to be present in an amount necessary to make the resin water-soluble or water-dispersible, and the dicarboxylic acid having a sulfonate group is 2 mol% to 20 mol% in the dicarboxylic acid. It is preferable to use within a range. By setting the amount of the sulfonate group in the range of 2 mol% to 20 mol%, water solubility or water dispersibility is sufficient, water resistance after application is not inferior, and the films can be prevented from sticking to each other. .

  In the acrylic resin, a compound having a carboxyl group and / or a salt thereof is copolymerized by 3 to 40% by weight, preferably 3 to 30% by weight, more preferably 4 to 25% by weight. It is desirable. If the amount of copolymerization is less than this, the adhesion to the substrate 2 and the dye layer 4 cannot be stably obtained, and if it exceeds this, the adhesion to the substrate 2 and the dye layer 4 deteriorates conversely. .

  Examples of the compound having a carboxyl group and / or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid and / or a salt thereof (ammonium salt, lithium salt, sodium salt, potassium salt, Amine salts and the like). Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of easy adhesion, and acrylic acid is particularly preferable.

  A well-known thing can be used as a monomer component which comprises an acrylic resin. For example, alkyl acrylate, alkyl methacrylate (the alkyl group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, lauryl group, stearyl group, Cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.), hydroxy group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide Amide group-containing monomers such as N-methoxymethylmethacrylamide and N-phenylacrylamide, amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate, and epoxy groups such as glycidyl acrylate and glycidyl methacrylate Containing monomers and the like can be mentioned, and these are copolymerized using one or more kinds. Furthermore, these can be used in combination with other types of monomers.

  Other types of monomers include, for example, epoxy group-containing monomers such as allyl glycidyl ether, sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.) Monomers containing such salts, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid mono ester, acrylonitrile, methacrylonitrile, alkyl itaconic acid mono Examples include esters, vinylidene chloride, vinyl acetate, and vinyl chloride.

  As the acrylic resin, a modified polyester copolymer such as a block copolymer modified with acrylic, urethane, epoxy, or the like, a graft copolymer, or the like can also be used.

  The molecular weight of the acrylic resin is preferably 100,000 or more, more preferably 300,000 or more from the viewpoint of adhesion.

  As a preferable acrylic resin, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, and n-butyl acrylate are used as a basic skeleton, and 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and glycidyl methacrylate are copolymerized therewith. Things.

  In addition to the acrylic resin, a different acrylic resin can be used in combination. For example, since the acrylic resin usually has a glass transition point (Tg) as low as less than 50 ° C., an acrylic resin having a glass transition point (Tg) higher than this, for example, a glass transition point (Tg) of 50 ° C. or higher, More preferably, by using together an acrylic resin of 60 ° C. or higher, moisture-resistant adhesion can be further improved. Moreover, the mixing ratio of these different acrylic resins is not particularly limited.

  Examples of water-soluble or water-dispersible polyurethane resins include Japanese Patent Publication No. 42-24194, Japanese Patent Publication No. 46-7720, Japanese Patent Publication No. 46-10193, Japanese Patent Publication No. 49-37839, Japanese Patent Publication No. 53-. Known polyurethane resins can be used in Japanese Patent No. 126058, Japanese Patent Laid-Open No. 54-138098, Japanese Patent Laid-Open No. 58-78761, and the like. The main components of the polyurethane resin are polyisocyanate, polyol, chain extender, crosslinker and the like.

  Examples of polyisocyanates include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like.

  Examples of the polyol include polyether chain polyethylene adipate such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol, polyesters such as polycaprolactone, acrylic polyol, castor oil and the like.

  Examples of the chain extender or crosslinking agent include ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine, 4,4'-diaminodiphenylmethane, water and the like.

  The polyurethane-based resin having an anionic group includes a method of using a compound having an anionic group in a polyol, a polyisocyanate compound, a chain extender, etc., which are polyurethane-forming components, and an unreacted isocyanate group and an anionic group of the produced polyurethane. It can be produced using a method of reacting a compound having a specific compound or a method of reacting a group having active hydrogen of polyurethane with a specific compound.

  The polyurethane resin is preferably a resin comprising a polyol having a molecular weight of 300 to 20000, a polyisocyanate, a chain extender having a reactive hydrogen atom, a group that reacts with an isocyanate group, and a compound having at least one anionic group.

Examples of the anionic group in the polyurethane-based resin include lithium salts such as —SO ₃ H and —COOH, sodium salts, potassium salts, and magnesium salts. A sulfonate group is particularly preferable. The amount of the anionic group in the polyurethane resin is preferably 0.05% by weight to 5% by weight. By setting the amount of the anionic group to 0.05% by weight to 5% by weight, the water solubility or water dispersibility of the polyurethane-based resin is good, the anionic group is not excessive, and the water resistance after coating is high. The film can be prevented from adhering to each other due to moisture absorption.

  The fluorosurfactant contained in the primer layer 3 diffuses into the cyan dye layer 4C, suppresses crystallization of the cyan dye when the cyan dye is not transferred, and moves toward the substrate 2 when the cyan dye is thermally transferred. It suppresses the migration of the cyan dye, suppresses the fusion between the cyan dye layer 4C and the thermal transfer image receiving sheet, and the abnormal transfer of the cyan dye layer 4C.

  Such a fluorosurfactant preferably contains at least one of the following general formulas (2) to (4).

_{Rf- (L 1) m - (} Y 1) n -X ··· formula (2)
(In the general formula (2), Rf represents an aliphatic group containing at least one fluorine atom, L ₁ represents a divalent linking group, Y ₁ represents an alkyleneoxy group which may have a substituent, An alkylene group or an alkenyl group is represented, X represents a hydrogen atom, a hydroxyl group, an anionic group or a cationic group, m represents 0 or an integer of 1 to 5, and n represents 0 or an integer of 1 to 40. )

_{Rf- (O-Rf ') n1} -L 2 -X' m1 ··· general formula (3)
(In the general formula (3), Rf represents an aliphatic group containing at least one fluorine atom, Rf ′ represents an alkylene group containing at least one fluorine atom, and L ₂ represents a simple bond or linking group. X ′ represents a hydroxyl group, an anionic group, or a cationic group, and n1 and m1 each represents an integer of 1 or more.)

_{[(Rf "O) n2 - (} PFC) -CO-Y 2 ] _k -L _{3 -X" m2} ··· formula (4)
(In General Formula (4), Rf ″ represents a perfluoroalkyl group containing 1 to 4 carbon atoms, (PFC) represents a perfluorocycloalkylene group, and Y ₂ represents a linkage containing an oxygen atom or a nitrogen atom. L ₃ represents a simple bond or linking group, X ″ represents an anionic group, a cationic group, a nonionic group, or a water-solubilizing polar group containing an amphoteric group, and n2 represents 1 to 5 Represents an integer, k represents an integer of 1 to 3, and m2 represents an integer of 1 to 5.)

  In general formula (2) and general formula (3), Rf represents an aliphatic group containing at least one fluorine atom, and the aliphatic group preferably has 1 to 18 carbon atoms, Furthermore, it is preferable that carbon number is 2-12, and it is especially preferable that carbon number is 3-7.

In the general formula (2), L ₁ represents a divalent linking group, and the divalent linking group is particularly preferably a sulfonamide group, an alkylene oxide group, a phenoxy group, or an alkylenecarbonyl group.

In the general formula (2), Y ₁ represents an alkyleneoxy group or an alkylene group which may have a substituent. Examples of the alkyleneoxy group include an ethyleneoxy group and a propyleneoxy group. preferable. Moreover, as an alkylene group, a methylene group, ethylene group, a propylene group, etc. are mentioned, An ethylene group is especially preferable.

  In the general formula (2), X represents a hydrogen atom, a hydroxyl group, an anionic group or a cationic group, and the anionic group is preferably a carboxyl group, a sulfonic acid group or a phosphoric acid group. As the cation, alkali metal ions such as sodium ion and potassium ion, ammonium ion and the like are preferable. The cationic group is preferably a quaternary alkylammonium group, and the counter anion of the cationic group is preferably a halide ion or p-toluenesulfonic acid ion, and more preferably a p-toluenesulfonic acid ion. .

  In the general formula (2), m represents 0 or an integer of 1 to 5, and n represents 0 or an integer of 1 to 40, and it is particularly preferable that m is 0 and n is 10 to 20. .

  In the general formula (3), Rf ′ represents an alkylene group containing at least one fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, particularly 2 or 3 is preferred.

In the general formula (3), L ₂ represents a simple bond or a linking group, and the linking group is preferably an alkylene group, an arylene group, or a divalent linking group containing a hetero atom.

  In the general formula (3), X ′ represents a hydroxyl group, an anionic group or a cationic group, and the anionic group is preferably a carboxyl group, a sulfonic acid group or a phosphoric acid group. Is preferably an alkali metal ion such as sodium ion or potassium ion, or an ammonium ion. Further, the cationic group is preferably a quaternary alkylammonium group, and the counter anion of the cationic group is preferably a halide ion, p-toluenesulfonic acid ion or the like.

  In the general formula (3), n1 and m1 each represent an integer of 1 or more, and n1 is preferably 1 or more and 10 or less, and m1 is preferably 1 or more and 3 or less.

  In the general formula (4), Rf ″ represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the perfluoroalkyl group is particularly preferably a trifluoromethyl group.

  In the general formula (4), (PFC) represents a perfluorocycloalkylene group. Examples of the perfluorocycloalkylene group include a perfluorocyclooctylene group, a perfluorocycloheptylene group, and a perfluorocyclohexylene group. And a perfluorocyclopentylene group, and a perfluorocyclohexylene group is particularly preferable.

In General Formula (4), Y ₂ represents a linking group containing an oxygen atom or a nitrogen atom, and the linking group is particularly preferably —OCH ₂ — or —NHCH ₂ —.

In the general formula (4), L ₃ represents a simple bond or a linking group, and as the linking group, a substituted or unsubstituted alkylene (for example, ethylene, n-propylene, or isobutylene), arylene (for example, phenylene) A multivalent, generally two, such as a combination of alkylene and arylene (eg, xylylene), oxydialkylene (eg, CH ₂ CH ₂ OCH ₂ CH ₂ ), thiodialkylene (eg, CH ₂ CH ₂ SCH ₂ CH ₂ ) Valent linking group.

In the general formula (4), X ″ represents an anionic group, a cationic group, a nonionic group, or a water-solubilizing polar group containing an amphoteric group. Examples of the anionic group include CO ₂ H, CO ₂ M, SO ₃ H, SO ₃ M, OSO ₃ H, OSO ₃ M, (OCH ₂ CH ₂ ) OSO ₃ M, OPO (OH) ₂ , and OPO (OM) ₂ , where M is sodium, potassium, or calcium Among them, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are preferable. Examples of the counter cation of the anionic group include sodium ions and potassium ions. Preferred are alkali metal ions, ammonium ions, etc. As the cationic group, a quaternary alkyl ammonium group is preferred, and the cationic group The counter anion is preferably a halide ion, p-toluenesulfonic acid ion, etc. The nonionic group is preferably a hydroxyl group.

  Specific examples of the fluorosurfactant that can be used in the present invention are illustrated below, but the present invention is not limited thereto.

Example of fluorinated surfactant represented by formula (2) 1-1. C ₈ F ₁₇ SO ₃ K
1-2. C ₈ F ₁₇ SO ₃ Li
1-3. C ₈ F ₁₇ COONH ₄
1-4. C ₈ F ₁₇ COOK
1-5. C ₈ F ₁₅ SO ₃ K
1-6. C ₈ F ₁₅ SO ₃ Li
1-7. C ₈ F ₁₅ COONH ₄
1-8. C ₈ F ₁₅ COOK
1-9. _{C 9 F 19 -O-C 6} H 4 -SO 3 K
1-10. _{C 9 F 19 -O-C 6} H 4 -SO 3 Na
1-11. _{C 9 F 17 -O-C 6} H 4 -SO 3 K
1-12. _{C 9 F 17 -O-C 6} H 4 -SO 3 Na
1-13. _{C 6 F 13 -O-C 6} H 4 -SO 3 K
1-14. _{C 6 F 13 -O-C 6} H 4 -SO 3 Na
1-15. _{C 6 F 11 -O-C 6} H 4 -SO 3 K
1-16. _{C 6 F 11 -O-C 6} H 4 -SO 3 Na
1-17. C ₇ F ₁₅ COONH ₄
1-18. C ₇ F ₁₃ COONH ₄
1-19. NaO ₃ S (CH (CHCOOCH ₂ CH ₂ C ₈ F ₁₇ ) COOCH ₂ CH ₂ C ₈ F ₁₇ )
1-20. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 COOK)
1-21. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 OPO 3 Na 2)
1-22. _{C 8 F 17 SO 2 N (} C 12 H 25) ((C 2 H 4 O) 4 C 4 H 8 SO 3 Na)
1-23. C ₆ F ₁₃ CH ₂ CH ₂ SO ₃ NH ₄
1-24. CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ SO ₃ NH ₄
1-25. CF ₃ CF ₂ (CF ₂ CF ₂ ) ₄ CH ₂ CH ₂ SO ₃ NH ₄
1-26. _{C 6 F 13 CH 2 CH 2} O-PO (ONH 4) 2
1-27. _{C 6 F 3 CH 2 CH 2} O-PO (ONH 4) (OCH 2 CH 2 OH)
1-28. C ₂ F ₅ (CH ₂ ) ₆ SO ₃ NH ₄
1-29. _{C 3 F 7 (CH 2)} 5 SO 3 NH 4
1-30. C ₂ F ₅ (CH ₂ ) ₆ COOLi
1-31. _{C 3 F 7 (CH 2)} 3 O-C 6 H 4 -SO 3 K
1-32. NaO ₃ S (CH (CHCOO (CH ₂ ) ₉ C ₃ F ₇ ) COO (CH ₂ ) ₉ C ₃ F ₇ )
1-33. _{C 3 F 7 (CH 2)} 5 SO 2 N (C 3 H 7) (CH 2 COOK)
1-34. _{C 3 F 7 (CH 2)} 5 SO 2 N (C 12 H 25) ((C 2 H 4 O) 4 C 4 H 8 SO 3 Na)
1-35. _{(C 2 F 5 CH 2 O} ) 2 PO (OH) 2
1-36. _{C 3 F 7 CH 2 CH 2} OPO (OH) 2
1-37. C ₃ F ₇ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi
1-38. C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi
1-39. _{(C 6 F 13 CH 2 CH} 2 O) 2 PO (OH) 2
1-40. _{C 6 F 13 CH 2 CH 2} O- (CH 2 CH 2 O) 10 -H
1-41. _{C 8 F 17 CH 2 CH 2} O- (CH 2 CH 2 O) 12 -H
1-42. _{C 10 F 21 CH 2 CH 2} O- (CH 2 CH 2 O) 8 -H
1-43. _{C 4 F 9 CH 2 CH 2} O- (CH 2 CH 2 O) 20 -H
1-44. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 10 -H
1-45. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 12 -H
1-46. _{C 2 F 5 CH 2 CH 2} O- (CH 2 CH 2 O) 15 -H
1-47. _{C 3 F 7 - (CH 2} CH 2 O) 2 - (CH 2 C (OH) H-CH 2 O) 10 -H
1-48. _{C 4 F 9 -CH (CH 3} ) CH 2 O- (CH 2 CH 2 O) 9 -H
1-49. _{C 6 F 13 - (CH 2} CH 2 O) 3 - (CH 2 C (OH) H-CH 2 O) 12 -H
1-50. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 31 -H

Example of fluorinated surfactant represented by general formula (3) 2-1. C ₅ F ₁₁ (OCF ₂ ) OPO (ONa) ₂
2-2. HC ₆ F ₁₂ (OCF ₂ ) OPO (ONa) ₂
2-3. C ₈ F ₁₇ (OCF ₂ ) OPO (ONa) ₂
2-4. C ₁₀ F ₂₁ (OCF ₂ ) OPO (ONa) ₂
2-5. _{C 12 F 25 (O-CF} 2) OPO (ONa) 2
2-6. C ₃ F ₇ (OC ₂ F ₄ ) OPO (ONa) ₂
2-7. C ₄ F ₉ (OC ₂ F ₄ ) OPO (ONa) ₂
2-8. C ₅ F ₁₁ (OC ₂ F ₄ ) OPO (ONa) ₂
2-9. _{H-C 6 F 12 - (} OC 2 F 4) -OPO (ONa) 2
2-10. C ₇ F ₁₅ (OC ₂ F ₄ ) OPO (ONa) ₂
2-11. C ₉ F ₁₉ (OC ₂ F ₄ ) OPO (ONa) ₂
2-12. C ₁₁ F ₂₃ (OC ₂ F ₄ ) OPO (ONa) ₂
2-13. C ₃ F ₇ (OCF ₂ ) ₆ OPO (ONa) ₂
2-14. C ₄ F ₉ (OCF ₂ ) ₆ OPO (ONa) ₂
2-15. _{C 5 F 11 - (O-} CF 2) 5 -O-PO (ONa) 2
2-16. _{H-C 6 F 12 - (} OCF 2) 3 OPO (ONa) 2
2-17. C ₃ F ₇ O (CF ₂ ) ₃ COONa
2-18. C ₄ F ₉ O (CF ₂ ) ₃ COONa
2-19. C ₅ F ₁₁ O (CF ₂ ) ₃ COONa
2-20. _{H-C 7 F 14} - [O _{(CF 2) 3]} -OCH _{(COONa) 2}
2-21. C ₈ F ₁₇ O (CF ₂ ) ₃ OCH (COONa) ₂
2-22. C ₃ F ₇ O (CF ₂ ) ₅ COONa
2-23. C ₄ F ₉ O (CF ₂ ) ₅ COONa
2-24. C ₅ F ₁₁ O (CF ₂ ) ₅ COONa
2-25. C ₇ F ₁₅ O (CF ₂ ) ₅ COONa
2-26. C ₃ F ₇ (OC ₂ F ₄ ) ₅ COONa
2-27. C ₄ F ₉ (OC ₂ F ₄ ) ₂ COONa
2-28. _{C 5 F 11 - (O-} C 2 F 4) 2 -COONa
2-29. _{H-C 7 F 14 (OC} 2 F 4) 2 COONa
2-30. C ₉ F ₁₉ (OC ₂ F ₄ ) ₂ COONa
2-31. C ₂ F ₅ (OC ₂ F ₄ ) ₃ COONa
2-32. C ₂ F ₅ (OC ₂ F ₄ ) ₅ COONa
2-33. C ₃ F ₇ (OC ₂ F ₄ ) ₄ COONa
2-34. C ₄ F ₉ (OC ₂ F ₄ ) ₃ COONa
2-35. C ₅ F ₁₁ (OC ₂ F ₄ ) ₃ NHCOCH (COONa) ₂
2-36. HC ₆ F ₁₂ (OC ₂ F ₄ ) ₃ NHCOCH (COONa) ₂
2-37. C ₄ F ₉ (OC ₂ F ₄ ) ₂ OCF ₂ COONa
2-38. C ₅ F ₁₁ (OC ₂ F ₄ ) ₂ OCF ₂ COONa
2-39. C ₇ F ₁₅ (OC ₂ F ₄ ) ₂ OCF ₂ COONa
2-40. C ₄ F ₉ -OCF ₂ - [O _{(CF 2) 5]} -COOK
2-41. C ₅ F ₁₁ -OCF ₂ - [O _{(CF 2) 5]} -COOK
2-42. _{H-C 6 F 12 -OCF 2} - [O _{(CF 2) 5]} -COOK
2-43. _{C 4 F 9 - (OC 2} F 4) 5 - [O _{(CF 2) 3]} -COOK
2-44. _{C 5 F 11 - (OC 2} F 4) 2 - [O _{(CF 2) 3]} -COOK
2-45. _{C 6 F 13 - (OC 2} F 4) 2 - [O- _{(CF 2) 3]} -COOK
2-46. C ₁₂ F ₂₅ OCF ₂ OSO ₃ Na
2-47. C ₇ F ₁₅ OC ₂ F ₄ OC ₃ H ₆ SO ₃ Na
2-48. _{C 4 F 9 - (OCF 2} ) 6 -OSO 3 Na
2-49. _{H-C 5 F 10 - (} OCF 2) 5 -OC 3 H 6 SO 3 Na
2-50. _{H-C 6 F 12 - (} OCF 2) 3 -OSO 3 Na
2-51. _{C 5 F 11 - (OC 2} F 4) 2 -OC 3 H 6 SO 3 Na
2-52. _{C 7 F 15 - (OC 2} F 4) 2 -OSO 3 Na
2-53. _{C 3 F 7 - (OC 2} F 4) 4 -OC 3 H 6 -SO 3 Na
2-54. _{C 4 F 9 - (OC 2} F 4) 3 -O-SO 3 Na
2-55. _{H-C 5 F 10 - (} OC 2 F 4) 3 -OC 3 H 6 -SO 3 Na
2-56. C ₅ F ₁₁ OCF ₂ - [O _{(CF 2) 5]} -OSO ₃ Na
2-57. _{C 4 F 9 - (OC 2} F 4) 2 - [O _{(CF 2) 3]} -OSO ₃ Na
2-58. _{(HCF 2) 3 C- (OC} 2 F 4) 3 -OSO 3 Na
2-59. _{(CF 3) 2 CFCF 2 CF} 2 - (OCF 2) 5 -OC 3 H 6 -SO 3 Na
2-60. C ₁₁ F ₂₃ (OC ₂ F ₄ ) OSO ₃ Na
2-61. _{C 4 F 9 - (OC 2} F 4) 3 -NHCO- (CH 2) 3 -N + (CH 3) 3 · Br -
2-62. _{C 5 F 11 - (OC 2} F 4) 2 -NHCO- (CH 2) 3 -N + (CH 3) 3 · Br -
2-63. _{HC 6 F 12 - (OC 2} F 4) 2 -NHCO- (CH 2) 3 -N + (CH 3) 3 · Br -
2-64. _{C 4 F 9 - (OC 2} F 4) 3 -OCH 2 -N + (CH 3) 2 (C 2 H 4 OH) · Br -
2-65. _{C 5 F 11 - (OC 2} F 4) 2 -OCH 2 -N + (CH 3) 2 (C 2 H 4 OH) · Br -
2-66. _{HC 6 F 12 - (OC 2} F 4) 2 -OCH 2 -N + (CH 3) 2 (C 2 H 4 OH) · Br -
2-67. _{C 5 F 11 -OCF 2 - (} OC 2 F 4) -NHCO- (CH 2) 3 -N + (CH 3) 3 · Br -
2-68. _{(CF 3) 3 C- (OC} 2 F 4) 3 -OCH 2 -N + (CH 3) 2 (C 2 H 4 OH) · Br -
2-69. C ₁₂ F ₂₅ OCF ₂ OH
2-70. C ₇ F ₁₅ OC ₂ F ₄ OH
2-71. _{C 4 F 9 - (OCF 2} ) 6 -OC 3 H 6 OH
2-72. _{C 5 F 11 - (OCF 2} ) 5 -OC 3 H 6 OH
2-73. _{HC 6 F 12 - (OCF 2} ) 3 -OH
2-74. _{C 5 F 11 - (OC 2} F 4) 2 -OC 3 H 6 OH
2-75. _{C 7 F 15 - (OC 2} F 4) 2 -OC 3 H 6 OH
2-76. _{C 3 F 7 - (OC 2} F 4) 4 -OC 3 H 6 OH
2-77. _{HC 4 F 8 - (OC 2} F 4) 3 -OC (C 2 H 4 OH) 3
2-78. _{C 5 F 11 - (OC 2} F 4) 3 -OC 3 H 6 OH
2-79. C ₅ F ₁₁ OCF ₂ O (CF ₂ ) ₅ OH
2-80. _{C 4 F 9 - (OC 2} F 4) 2 -O (CF 2) 3 OH
2-81. _{(CF 3) 3 C- (OC} 2 F 4) 3 -OH
2-82. _{(HCF 2) 2 CFCF 2 CF} 2 - (OCF 2) 5 -OH
2-83. C ₁₁ F ₂₃ (OC ₂ F ₄ ) ₄ OH

  Regarding the method for synthesizing the compound represented by the general formula (3), JP-T-10-500950 and JP-A-11-50436 can be referred to.

Example of fluorinated surfactant represented by general formula (4) 3-1. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 COO -
3-2. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 SO 3 -
3-3. ^{_{(CF 3 O) - (PFC}} ) -CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 SO 3 -
3-4. _{(CF 3 O) 3 - (} PFC) -CON (C 3 H 6 SO 3 -) C 3 H 6 N + (CH 3) 2 H
3-5. _{(CF 3 O) - (PFC} ) -CON (C 3 H 6 SO 3 -) C 3 H 6 N + (CH 3) 2 H
3-6. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 CH-CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 SO 3 -
3-7. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 CH-CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 SO 3 -
3-8. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 CH-CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 SO 3 -
3-9. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 N + (CH 3) 2 C 2 H 4 OH · Cl -
3-10. (CF ₃ O) _2- (PFC) -CONHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ C ₂ H ₄ OH · Cl ⁻
3-11. (CF ₃ O)-(PFC) -CONHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ C ₂ H ₄ OH · Cl ⁻
3-12. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 N + (CH 3) 2 H · Cl -
3-13. _{(CF 3 O) 2 - (} PFC) -CONHC 3 H 6 N + (CH 3) 2 H · Cl -
3-14. (CF ₃ O)-(PFC) -CONHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ H · Cl ⁻
3-15. [(CF ₃ O) _3- (PFC) -COOCH ₂ ] ₂ C (CH ₃ ) N ⁺ (CH ₃ ) ₂ H · Cl ⁻
3-16. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 C (CH 3) N + (CH 3) 2 H · Cl -
3-17. [(CF ₃ O)-(PFC) -COOCH ₂ ] ₂ C (CH ₃ ) N ⁺ (CH ₃ ) ₂ H · Cl ⁻
3-18. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 CHC 3 H 6 N + (CH 3) 2 H · Cl -
3-19. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 CHC 3 H 6 N + (CH 3) 2 H · Cl -
3-20. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 CHC 3 H 6 N + (CH 3) 2 H · Cl -
3-21. _{(CF 3 O) 3 - (} PFC) -COO (C 2 H 4 O) 12 H
3-22. _{(CF 3 O) 2 - (} PFC) -COO (C 2 H 4 O) 12 H
3-23. _{(CF 3 O) - (PFC} ) -COO (C 2 H 4 O) 12 H
3-24. _{(CF 3 O) 3 - (} PFC) -COO (C 2 H 4 O) 15 CH 3
3-25. _{(CF 3 O) 2 - (} PFC) -COO (C 2 H 4 O) 15 CH 3
3-26. _{(CF 3 O) - (PFC} ) -COO (C 2 H 4 O) 15 CH 3
3-27. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 CHC 3 H 6 OH
3-28. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 CHC 3 H 6 OH
3-29. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 CHC 3 H 6 OH
3-30. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 COONa
3-31. _{(CF 3 O) 2 - (} PFC) -CONHC 3 H 6 COONa
3-32. (CF ₃ O)-(PFC) -CONHC ₃ H ₆ COOK
3-33. _{(CF 3 O) 3 - (} PFC) -CONHC 3 H 6 SO 3 Na
3-34. _{(CF 3 O) 2 - (} PFC) -CONHC 3 H 6 SO 3 Na
3-35. _{(CF 3 O) - (PFC} ) -CONHC 3 H 6 SO 3 K
3-36. _{(CF 3 O) 3 - (} PFC) -CON (C 3 H 6 SO 3 Na) C 3 H 7
3-37. _{(CF 3 O) 2 - (} PFC) -CON (C 3 H 6 SO 3 Na) C 3 H 7
3-38. _{(CF 3 O) - (PFC} ) -CON (C 3 H 6 SO 3 Na) C 3 H 7
3-39. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 C (CH 3) COONa
3-40. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 C (CH 3) COONa
3-41. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 C (CH 3) COONa
3-42. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 C (COONa) 2
3-43. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 C (COONa) 2
3-44. [(CF ₃ O)-(PFC) -COOCH ₂ ] ₂ C (COONa) ₂
3-45. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 C (CH 3) SO 3 Na
3-46. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 C (CH 3) SO 3 Na
3-47. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 C (CH 3) SO 3 Na
3-48. _{[(CF 3 O) 3 -} (PFC) -COOCH 2] 2 CHC 3 H 6 SO 3 Na
3-49. _{[(CF 3 O) 2 -} (PFC) -COOCH 2] 2 CHC 3 H 6 SO 3 Na
3-50. _{[(CF 3 O) - (} PFC) -COOCH 2] 2 CHC 3 H 6 SO 3 Na

However, in the above, the substitution position of (PFC) represents a perfluoro-cyclohexylene group, _(CF 3 O), as a 1-position of the carbonyl _group, a 3,4,5-position in the case of _{(CF 3 O)} 3 , (CF ₃ O) ₂ is the 3rd and 4th positions, and (CF ₃ O) is the 4th position.

  Regarding the method for synthesizing the compound represented by the general formula (4), JP-A-10-158218 and JP-A-2000-505803 can be referred to.

As a fluorine-type surfactant contained in the primer layer 3, the fluorine-type surfactant with a perfluoro alkenyl structure is preferable, and about 10-300 microgram / m < ² > is preferable in the primer layer 3, 50-150 microgram / m < ² > is. More preferred. By making the content of the fluorosurfactant in the primer layer 3 about 10 to 300 μg / m ² , the effect is good and the induction of coating failures such as repellency and coating unevenness is suppressed during coating. It is preferable because it can

  Specific examples of commercially available fluorosurfactants that are preferable for the present invention include, for example, Footent 100C, Footent 150, Footent 250, Footent 300, Footent 400SW (manufactured by Neos), Novec HFE, Novec EGC-1700, Novec 1720 (manufactured by 3M), Zonyl, Zonyl FS (manufactured by DuPont), etc. can be obtained from the market, and any of them can be used in the present invention.

  In addition to the resin and the fluorosurfactant, the primer layer 3 may be, for example, silica (colloidal silica), alumina or hydrated alumina (alumina sol, colloidal alumina, cationic aluminum oxide or Its hydrates, suspicious boehmite, etc.), inorganic fine particles such as aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, titanium oxide, etc., and the coating properties and antistatic properties of the undercoat liquid forming the primer layer 3 It is also preferable to use a conventionally known cationic surfactant, anionic surfactant or the like for the purpose of imparting a function.

  The primer layer 3 is formed by, for example, applying a subbing solution containing a resin or a fluorosurfactant to a polyester film before completion of crystal orientation, and forming the crystal orientation by stretching and heat treatment. This is particularly preferable because heat treatment at a high temperature is possible and a uniform and thin primer layer 3 can be obtained. When the primer layer 3 is laminated by this method, an acrylic resin that can be dissolved, emulsified or suspended in water is preferable from the viewpoint of environmental pollution and explosion-proof properties. Such an acrylic resin is a reactive emulsifier or an interface. Prepared by a known method such as emulsion polymerization using an activator, suspension polymerization, soap-free polymerization, copolymerization with a monomer having a hydrophilic group (such as acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and its salt). be able to.

  On the primer layer 3, at least a cyan dye layer 4C is formed, and a yellow dye layer 4Y and a magenta dye layer 4M are formed as necessary.

  The cyan dye layer 4C is formed mainly of a cyan dye and a binder resin that supports the dye.

  The cyan dye is an indoaniline cyan dye represented by the following general formula (1).

（式中、Ｒ１及びＲ２は、置換又は非置換のアルキル基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、又は置換又は非置換のアリール基が好ましく、より好ましくはエチル基もしくはプロピル基である。Ｒ３、Ｒ４、Ｒ５およびＲ６は、水素原子、ハロゲン原子、シアノ基、水酸基、置換又は非置換のアルキル基、置換又は非置換のアルコキシ基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、置換又は非置換のアリール基、置換又は非置換のアシル基、置換又は非置換のアシルアミノ基、又は置換又は非置換のスルホニルアミノ基を好ましく、その中でもＲ３、Ｒ４、Ｒ５およびＲ６が水素原子、もしくはＲ３、Ｒ６のいずれか一つがメチル基、もう片一方が水度原子、かつＲ４、Ｒ５が水素原子のものが好ましい。Ｒ７は、水素原子が好ましい。Ｒ８は、水素原子又は置換又は非置換のアルキル基が好ましく、具体的には水素原子、メチル基、エチル基のいずれかが好ましい。Ｒ９は、水素原子又はハロゲン原子が好ましい。Ｒ１０は、置換又は非置換のアルキル基、置換又は非置換のシクロアルキル基、置換又は非置換のアラルキル基、置換又は非置換のアリール基、又は置換又は非置換のアルコキシ基が好ましく、具体的にはメチル基がより好ましい。）

(Wherein R1 and R2 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, more preferably an ethyl group. R3, R4, R5 and R6 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group. A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acylamino group, or a substituted or unsubstituted sulfonylamino group, among which R3, R4 , R5 and R6 are hydrogen atoms, or any one of R3 and R6 is a methyl group, the other is a water atom, and R4 and R5 are R7 is preferably a hydrogen atom, R8 is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, specifically a hydrogen atom, a methyl group, or an ethyl group. Is preferably a hydrogen atom or a halogen atom, and R10 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. A substituted alkoxy group is preferable, and a methyl group is more preferable.

  Specific examples of indoaniline-based cyan dyes that can be used for the cyan dye layer 4C are illustrated below, but are not limited thereto.

  It should be noted that the cyan dye layer 4C has other conventionally known thermal sublimation transfer type thermal transfer to the indoaniline pigment for the purpose of suppressing crystallization of the dye, adjusting the hue, and improving various storability. A dye having a structure such as azo, azomethine, methine, anthraquinone, quinophthalone, or naphthoquinone used in the recording sheet may be mixed.

  As the binder resin carrying the cyan dye, conventionally known binder resins used in thermal transfer recording ink sheets can be used. For example, cellulose addition compounds, cellulose esters, cellulose ethers such as cellulose ether, polyvinyl alcohol, etc. , Polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl acetate, polyacetic acid-polyvinyl chloride copolymer, polyacrylamide, styrene resin, poly (meth) acrylic acid ester, poly Examples thereof include vinyl resins such as (meth) acrylic acid and (meth) acrylic acid copolymers, rubber resins, ionomer resins, olefin resins, and polyester resins. Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resin having excellent storage stability is preferable.

As the binder resin of the cyan dye layer 4C, further, a reaction between an isocyanate described in JP-B-5-78437 and a compound having active hydrogen selected from polyvinyl butyral, polyvinyl formal, polyester polyol, and acrylic polyol. The reaction product is an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the reaction product in which the product, isocyanate is diisocyanate or triisocyanate, and the compound having active hydrogen;
An organic solvent-soluble polymer obtained by esterifying and / or urinating an intramolecular hydroxyl group of a natural and / or semi-synthetic water-soluble polymer; a natural and / or semi-synthetic water-soluble polymer;
Cellulose acetate having an acetylation degree of 2.4 or more and a total substitution degree of 2.7 or more described in JP-A-3-264393;
Polyvinyl alcohol (Tg = 85 ° C.), polyvinyl acetate (Tg = 32 ° C.), vinyl resin such as vinyl chloride / vinyl acetate copolymer (Tg = 77 ° C.), polyvinyl butyral (Tg = 84 ° C.), polyvinyl acetoacetal Polyvinyl acetal resins such as (Tg = 110 ° C.), vinyl resins such as polyacrylamide (Tg = 165 ° C.), polyester resins such as aliphatic polyester (Tg = 130 ° C.), etc .;
A reaction product of isocyanates described in JP-A-7-52564 and polyvinyl butyral containing 15-40% by weight of the vinyl alcohol moiety contained therein, and the isocyanates are diisocyanates or triisocyanates. Some of the above reaction products;
Phenylisocyanate-modified polyvinyl acetal resin of general formula (I) described in JP-A-7-32742;
One kind of isocyanate-reactive cellulose or isocyanate-reactive acetal resin described in JP-A-6-155935, isocyanate-reactive acetal resin, isocyanate-reactive vinyl resin, isocyanate-reactive acrylic resin, isocyanate A cured product of a composition containing one resin selected from a reactive phenoxy resin and an isocyanate-reactive styrol resin and a polyisocyanate compound;
Polyvinyl butyral resin (preferably having a molecular weight of 60,000 or more, glass transition temperature of 60 ° C. or more, more preferably 70 ° C. or more and 110 ° C. or less, and the mass% of the vinyl alcohol moiety in the polyvinyl butyral resin is 10 to 40%, preferably 15 to 30%));
Examples of the acrylic-modified cellulose resin and cellulose resin include cellulose resins (preferably ethyl cellulose) such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and butyric acetate cellulose.

  The various binder resins can be used alone or in combination of two or more thereof.

  Since the cyan dye layer 4C having such a structure is formed on the base material 2 via the primer layer 3, the fluorosurfactant in the primer layer 3 diffuses, and the fluorosurfactant Van der Waals forces between fluorine atoms and dye molecules, and fluorine-based surfactants with aromatic rings and indoaniline-based cyan dyes are mutually stabilized by π-π stacking interactions. In the case of thermal transfer, the interaction is weakened by the heat of the thermal head, thereby increasing the density expression. Further, at the time of thermal transfer, due to the exclusive action of the fluorine substituent, the peelability from the thermal transfer image receiving sheet is increased, the fusion between the cyan dye layer 4C and the thermal transfer image receiving sheet and the cyan dye layer 4C are sufficiently retained on the primer layer 3, Abnormal transfer that is transferred to the thermal transfer image receiving sheet together with the dye layer 4C is also suppressed. Further, it is possible to suppress the occurrence of so-called ground fogging in which the cyan dye is transferred to a white background area where the thermal energy of the thermal head is not applied and the cyan dye is not transferred.

  Similarly to the cyan dye layer 4C, the yellow dye layer 4Y and the magenta dye layer 4M, which are provided as necessary, are also formed mainly of a dye and a binder resin carrying the dye.

  Examples of the dye contained in the yellow dye layer 4Y and the magenta dye layer 4M include methine series such as diarylmethane series and thiazole series, indoaniline, acetophenone azomethine, azomethine series typified by pyridone azomethine, xanthene series, Oxazine, cyanomethylene represented by dicyanostyrene, azine, thiazine, benzeneazo, pyridoneazo, isothiazoleazo, imidazoleazo, pyrroleazo, disazo, triazoleazo and other azo, naphthoquinone, anthraquinone, quinophthalone And rhodamine lactam.

  Specifically, C.I. I. (Color Index) Disperse Yellow 3, 7, 23, 51, 54, 60, 79, 141, etc., C.I. I. (Color Index) Disperse thread 1, 59, 60, 73, 135, 167, etc., C.I. I. (Color Index) Disperse Violet 4, 1326, 31, 36, 56 etc., C.I. I. (Color Index) Disperse Orange 149, C.I. I. (Color Index) Solvent Yellow 14, 16, 29, 56, 201 etc., C.I. I. (Color Index) Solvent Red 18, 19, 23, 24, 25, 81, 143, 182, etc., C.I. I. (Color Index) Solvent Violet 13 etc. are mentioned.

  The dye content in each dye layer forming coating solution for forming the cyan dye layer 4C, the yellow dye layer 4Y and the magenta dye layer 4M is 5 to 90% by weight with respect to all the components constituting the dye layer 4. It is preferable to mix | blend with 10 to 70 weight%.

  Along with these dye layers 4, the releasable layer 5 provided on the one surface 2 a of the substrate 2 is provided between the primer layer 3 and the protective layer 6, and improves the peelability of the protective layer 6. When the releasability of the base material 2 and the protective layer 6 is not appropriate, the releasable layer 5 adjusts the adhesiveness between the base material 2 and the protective layer 6 and performs good release of the protective layer 6. Is provided.

  The release layer 5 includes, for example, various waxes such as silicone wax, silicone resin, fluorine resin, acrylic resin, water-soluble resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, polyvinyl acetal resin, acrylic vinyl ether. It is formed of various resins such as a resin based on maleic anhydride and a mixture thereof.

  The protective layer 6 laminated on the releasable layer 5 is heat transferable, and is heated by a heating means such as a thermal head, whereby a dye or the like of the heat transfer image receiving sheet is transferred onto a color image formed. It consists of a transparent resin layer that is transferred and covers and protects the surface of the color image.

  Examples of the resin that forms the protective layer 6 include polyester resins, polystyrene resins, acrylic resins, polyurethane resins, acrylic urethane resins, polycarbonate resins, epoxy-modified resins of these resins, and resins obtained by modifying these resins with silicone. And mixtures of these resins, ionizing radiation curable resins, ultraviolet blocking resins and the like. Preferred resins include polyester resin, polystyrene, acrylic resin, polycarbonate resin, and epoxy-modified resin.

  The protective layer 6 may further have an adhesive layer on the surface opposite to the releasable layer 5 and may have a two-layer structure. This adhesive layer is interposed between the protective layer 6 and the thermal transfer image receiving sheet when the protective layer 6 is transferred to the thermal transfer image receiving sheet, and serves to adhere the protective layer 6 to the color image. Improve the adhesion.

  As the resin constituting the adhesive layer, any resin containing a conventionally known pressure-sensitive adhesive, heat-sensitive adhesive, etc. can be used, and a thermoplastic resin having a glass transition temperature (Tg) of 30 to 80 ° C. Preferably there is. Specific examples of such thermoplastic resins include polyester resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, butyral resins, epoxy resins, polyamide resins, and vinyl chloride resins. The adhesive layer may contain additives such as an ultraviolet absorber, an antioxidant, and a fluorescent brightening agent.

  The heat-resistant slip layer 7 formed on the other surface 2b of the substrate 2 prevents thermal fusion between the heating means such as a thermal head and the substrate 2, and smoothly travels and adheres to the thermal head. It is provided for the purpose of removing.

  Examples of the resin used for the heat resistant slipping layer 7 include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, Polyvinyl resins such as polyvinyl acetal and polyvinyl pyrrolidone, acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, and acrylonitrile-styrene copolymer, polyimide resins, polyamide resins, polyamideimide resins, polyvinyltoluene resins, Used as a simple substance or a mixture of natural or synthetic resins such as coumarone indene resin, polyester resin, polyurethane resin, silicone-modified or fluorine-modified urethane It is. In order to further improve the heat resistance of the heat-resistant slipping layer 7, a resin having a hydroxyl group-based reactive group is used among the above resins, and a polyisocyanate or the like is used in combination as a crosslinking agent. It is preferable that

  Further, in order to impart slidability with the thermal head, a solid or liquid release agent or lubricant may be added to the heat-resistant slip layer 7 to provide heat-resistant slip. Examples of release agents or lubricants include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants. Activators, fluorine surfactants, metal soaps, organic carboxylic acids and derivatives thereof, fluorine resins, silicone resins, fine particles of inorganic compounds such as talc, silica, and the like can be used.

  The amount of lubricant contained in the heat-resistant slip layer 7 is about 5 to 50% by mass, preferably about 10 to 30% by mass. The thickness of the heat resistant slipping layer 7 can be about 0.1 to 10 μm, preferably about 0.3 to 5 μm.

  As a method for coating the dye layers 4Y, 4M, 4C, the release layer 5, the protective layer 6, the heat-resistant slip layer 7, and the adhesive layer, conventionally known methods are used. For example, gravure coating method, die coating method, roll coating method, rod bar coating method, air knife coating method, spray coating method, extrusion coating method, curtain coating method, or the hopper described in US Pat. No. 2,681,294 The extrusion coating method used is preferably used.

  The primer layer 3, the dye layers 4Y, 4M, and 4C, the releasable layer 5, the protective layer 6, the heat-resistant slip layer 7, and the adhesive layer described above are appropriately added with various additives such as wax and ultraviolet absorbers shown below. You may make it add.

Examples of the wax include polyethylene wax, polyester wax, polystyrene powder, olefin powder, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, wool wax, Examples include shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide.

  Examples of ultraviolet absorbers include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers. Specific examples include Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, and Tinuvin 328. Tinuvin 312, Tinuvin 315 (Ciba Geigy), Sumisorb-110, Sumisorb-130, Sumsorb-140, Sumisorb-200, Sumsorb-250, Sumisorb-300, Sumisorb-320, Sumisorb-340, 350 Sumisorb-400 (above, manufactured by Sumitomo Chemical Co., Ltd.), Mark LA-32, Mar LA-36, Mark 1413 (or more, Adeka Argus Chemical Co., Ltd.) can be obtained from the market under the trade name, etc., both can be used in the present invention.

  Further, a random copolymer having a Tg of 60 ° C. or higher, preferably 80 ° C. or higher, in which a reactive ultraviolet absorber and an acrylic monomer are randomly copolymerized may be used.

  The above-mentioned reactive ultraviolet absorber is a conventionally known salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, nickel chelate-based, hindered amine-based non-reactive ultraviolet absorber, for example, vinyl group, acryloyl group, Addition-polymerizable double bonds such as methacryloyl groups, or those having introduced an alcoholic hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group or the like can be used. Specifically, UVA635L, UVA633L (above, manufactured by BASF Japan Ltd.), PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like can be obtained from the market, and any of them can be used in the present invention. .

  The amount of the reactive ultraviolet absorbent in the random copolymer of the reactive ultraviolet absorbent and the acrylic monomer as described above is in the range of 10 to 90 mass%, preferably 30 to 70 mass%. The molecular weight of such a random copolymer can be about 5000 to 250,000, preferably about 9000 to 30000. The above-mentioned ultraviolet absorber and the random copolymer of the reactive ultraviolet absorber and the acrylic monomer may be contained alone or in combination. The addition amount of the random copolymer of the reactive ultraviolet absorber and the acrylic monomer is preferably 5 to 50% by mass with respect to the layer to be contained.

  In addition to the ultraviolet absorber, other light-proofing agents may be included. Here, the light-proofing agent is an agent that prevents or alters the degradation or decomposition of the dye by absorbing or blocking the action of degrading or decomposing the dye, such as light energy, thermal energy, and oxidizing action. In addition to UV inhibitors, antioxidants and light stabilizers conventionally known as additives for synthetic resins and the like can be mentioned. Also in that case, it may be contained in at least one of the release layer, the protective layer, and the adhesive layer, but is particularly preferably contained in the adhesive layer.

  Examples of the antioxidant include primary antioxidants such as phenols, monophenols, bisphenols, and amines, or secondary antioxidants such as sulfur and phosphorus. Examples of the light stabilizer include hindered amines.

  Although the usage-amount of the light-proofing agent containing said ultraviolet absorber is not specifically limited, Preferably it is 0.05-10 mass parts per 100 mass parts of resin which forms the layer to contain, Preferably it is 3-10 mass parts Use as a percentage. By making the usage-amount of a light-proofing agent 0.05-10 mass parts per 100 mass parts of resin, the effect as a light-proofing agent is acquired and it is not too much, and it does not become uneconomical.

  In addition to the above light-proofing agent, various additives such as a fluorescent brightening agent and a filler can be added to the adhesive layer in an appropriate amount at the same time.

  The thermal transfer image-receiving sheet to which the yellow, magenta, and cyan dyes and the protective layer 6 are transferred from the thermal transfer recording medium 1 having the above-described configuration is not shown in detail, but the dyes are formed on the support through the intermediate layer. A receiving layer is formed.

  Since the support has a role of holding the receiving layer and is heated at the time of thermal transfer, the support preferably has a mechanical strength that does not hinder handling even in a heated state.

  The material for such a support is not particularly limited. For example, condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality paper, art paper, coat Paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, poly Ether imide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, Li polyether sulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene-ethylene, tetrafluoroethylene-hexafluoropropylene, polychlorotrifluoroethylene, films such as polyvinylidene fluoride and the like. The support may be a white opaque film formed by adding a white pigment or a filler to these synthetic resins, or a foamed foam sheet, and is not particularly limited.

  Moreover, as a support body, the laminated body by arbitrary combinations can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper, or synthetic paper of cellulose synthetic paper and a plastic film. The thickness of these supports may be arbitrary and is usually about 10 to 300 μm.

  The support preferably has a layer having fine voids in order to have higher printing sensitivity and high image quality without density unevenness or white spots. As the layer having fine voids, a plastic film or synthetic paper having fine voids inside can be used. In addition, a layer having fine voids can be formed on various supports by various coating methods. As a plastic film or synthetic paper having fine voids, polyolefin, especially polypropylene, is mainly blended with an inorganic pigment and / or a polymer incompatible with polypropylene, and these are used as void (void) formation initiators. A plastic film or synthetic paper obtained by stretching and forming a mixture of the above is preferable. If these are mainly polyester, etc., the viscoelastic or thermal properties make the cushioning and heat insulation properties inferior to those mainly made of polypropylene. Unevenness is also likely to occur.

Considering these points, the elastic modulus at 20 ° C. of the plastic film and the synthetic paper is preferably 5 × 10 ⁸ Pa to 1 × 10 ¹⁰ Pa. In addition, since these plastic films and synthetic paper are usually formed by biaxial stretching, they shrink by heating. When these are left at 110 ° C. for 60 seconds, the shrinkage is 0.5 to 2.5%. The plastic film and the synthetic paper described above may be combined with each other as a single layer including fine voids, or may have a plurality of layers. In the case of a plurality of layer configurations, all layers constituting the layer may contain fine voids, or a layer having no fine voids may be contained. A white pigment may be mixed in the plastic film or synthetic paper as a concealing agent as necessary. In order to increase whiteness, an additive such as a fluorescent brightening agent may be included. The layer having fine voids preferably has a thickness of 30 to 80 μm.

  As the layer having fine voids, a layer having fine voids can be formed on the support by a coating method. As the plastic resin to be used, known resins such as polyester, urethane resin, polycarbonate, acrylic resin, polyvinyl chloride, and polyvinyl acetate can be used singly or in combination.

Further, if necessary, a resin such as polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, or polycarbonate is used on the surface of the support opposite to the side on which the image receiving layer is provided for the purpose of preventing curling. Or a layer of synthetic paper. As a bonding method, for example, known lamination methods such as dry lamination, non-solvent (hot melt) lamination, EC lamination method and the like can be used, but preferred methods are dry lamination and non-solvent lamination. Examples of the adhesive suitable for the non-solvent lamination method include Takenate 720L manufactured by Takeda Pharmaceutical Co., Ltd., and examples of the adhesive suitable for dry lamination include Takelac manufactured by Takeda Pharmaceutical Co., Ltd. Examples include A969 / Takenate A-5 (3/1), Polysol PSA SE-1400, Vinylol PSA AV-6200 series, manufactured by Showa High Polymer Co., Ltd., and the like. The amount of these adhesives, from about 1-8 g / ^{m 2} on a solids, and preferably from 2 to 6 g / ^{m 2.}

  When the plastic film and the synthetic paper as described above, or between them, or various papers and the plastic film or the synthetic paper are laminated, they can be bonded together by an adhesive layer.

  For the purpose of increasing the adhesive strength between the support and the thermal transfer image-receiving layer, various primer treatments and corona discharge treatments are preferably performed on the surface of the support.

  It is preferable that at least one intermediate layer is provided between the support and the image receiving layer. The intermediate layer means all layers provided between the image receiving layer and the substrate, such as an adhesive layer (primer layer), a barrier layer, an ultraviolet absorbing layer, a foamed layer, an antistatic layer, etc. Either can be used. Furthermore, it is preferable to add a white pigment such as titanium oxide to the intermediate layer in order to conceal the glare and unevenness of the support because the degree of freedom in selecting the support is widened. The content of the white pigment in the intermediate layer is preferably 30 to 300 parts by mass of the white pigment solid content with respect to 100 parts by mass of the resin solid content, but is used in the range of 100 to 300 parts by mass in order to improve the concealability. Further preferred.

  As the intermediate layer, a layer obtained by curing a thermoplastic resin, a thermosetting resin, or a thermoplastic resin having a functional group by using various additives or other methods can be used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, polyester, chlorinated polypropylene, modified polyolefin, urethane resin, acrylic resin, polycarbonate, ionomer, resin having a monofunctional and / or polyfunctional hydroxyl group-containing prepolymer cured with isocyanate or the like Etc. can be used.

  The image receiving layer is composed of a binder resin and, if necessary, various additives such as a release agent on one surface of the support.

  A well-known thing can be used for binder resin, It is preferable to use what a dye tends to dye. Specifically, polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene Resins, polyamide resins, phenoxy resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, polyurethane, polycarbonate, acrylic resins, ionomers, cellulose derivatives, etc., or mixtures thereof can be used. Of these, polyester resins and vinyl resins are preferred.

  It is preferable to add a release agent to the image receiving layer in order to prevent thermal fusion with the dye layer. As the mold release agent, a phosphoric ester plasticizer, a fluorine compound, silicone oil (including reaction curable silicone) and the like can be used, and among these, silicone oil is preferable. As the silicone oil, various modified silicones such as dimethyl silicone can be used. Specifically, amino-modified silicone, epoxy-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone, and the like can be used by blending them or polymerizing them using various reactions. One or more release agents are used. Further, the addition amount of the release agent is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the image receiving layer forming resin. By setting the addition amount of the release agent to 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin, it is possible to suppress the fusion between the thermal transfer recording medium 1 and the image receiving layer of the thermal transfer image receiving sheet or the decrease in printing sensitivity. These release agents may be provided as a separate release layer on the image receiving layer without being added to the image receiving layer.

  The image receiving layer is a reverse roll coating method using a bar coater, a gravure printing method, a screen printing method, a roll coating method, a gravure plate, a coating solution dissolved or dispersed in a solvent such as water or an organic solvent on a support. It can be formed by applying by an ordinary method such as air knife coating method, spray coating method, curtain coating method, extrusion coating method, and drying. The intermediate layer is formed by the same method as that for the image receiving layer.

  In addition, the image receiving layer is not only formed by directly applying the coating liquid on the support and drying as described above, but also by forming the image receiving layer in advance on another support and forming it on another support. The receptor layer thus formed may be transferred and formed on the support of the thermal transfer image-receiving sheet. Further, two or more layers can be simultaneously applied to each layer, and in particular, all the layers can be applied at one time.

  The thickness of the image receiving layer is the thickness after coating and drying, and is preferably about 0.1 to 10 μm.

  The thermal transfer image receiving sheet used in the present invention may be supplied to the thermal transfer printer as a single sheet or as a roll. The sheet supply refers to, for example, a form in which a thermal transfer image receiving sheet is cut into a certain size, about 50 sheets are put in a cassette and mounted on a thermal transfer printer. The roll form is a form in which the image-receiving sheet is supplied to the thermal transfer printer in that form, cut to a desired size after printing, and used. In particular, the latter is preferable because troubles in the conveyance system such as feeding failure and ejection failure such as inserting two sheets can be solved and the capacity of the printable sheet can be increased.

  When supplying the image receiving sheet in a roll form, especially when the postcard specification is as described above, or when using a thermal transfer image receiving sheet of a label or a seal type, a design mark such as a zip code frame formed on the back side In order to align the cutting position with the half-cut position of the seal, a detection mark may be provided on the back side.

  The yellow dye layer 4Y, the magenta dye layer 4M, and the cyan dye layer 4C of the thermal transfer recording medium 1 described above are sequentially heated by the heating means such as a thermal head to the dye receiving layer of the thermal transfer image receiving sheet as described above. After the yellow, magenta and cyan dyes are transferred and the dyes are retained by the dye receiving layer and a color image is formed, the protective layer 6 is heated and peeled off at the interface with the release layer 5. The protective layer 6 can be transferred onto the color image to form a color image protected by the protective layer 6.

  In the thermal transfer recording medium 1, a primer layer 3 containing a fluorosurfactant is formed on a substrate 2, and a yellow dye layer 4Y, a magenta dye layer 4M, and a cyan dye are formed on the primer layer 3. The layer 4C is formed, and among these, in the cyan dye layer 4C containing the indoaniline cyan dye represented by the general formula (1), the fluorine-based surfactant diffuses into the primer layer 3. The fluorosurfactant can suppress the crystallization of the cyan dye before the thermal transfer, and can enhance the density expression during the thermal transfer. Further, at the time of thermal transfer, due to the exclusive action of the fluorine substituent, the releasability from the thermal transfer image receiving sheet increases, and the cyan dye layer 4C and the thermal transfer image receiving sheet are fused, or the cyan dye layer 4C is transferred to the thermal transfer image receiving sheet. Transcription is also suppressed. Further, in the thermal transfer recording medium 1, it is possible to suppress the occurrence of so-called ground fogging in which the cyan dye is transferred to a white background area where the thermal energy of the thermal head is not applied and the cyan dye is not transferred.

  As a result, the thermal transfer recording medium 1 can form a high-density and high-quality image. Further, even if high-speed printing is performed, the cyan dye layer 4C and the thermal transfer image-receiving sheet are fused or abnormally transferred. Therefore, it is possible to form a high-quality image with a high density, and it is possible to meet the demands for increasing the printing speed of thermal transfer, and increasing the density and quality of thermal transfer images.

  Hereinafter, the thermal transfer recording medium to which the present invention is applied will be specifically described with reference to Examples and Comparative Examples.

<Example 1>
In Example 1, first, as a base material, a back surface layer (heat resistant slipping layer) having a composition shown in Table 1 below was formed on one surface of a polyethylene terephthalate film having a thickness of 4.5 μm (product name: Lumirror Toray Co., Ltd.). ) The coating solution was applied by die coating so that the dry film thickness was 0.5 μm, dried, and cured at 50 ° C. for 5 days to form a back layer. On the other surface, a primer layer having the composition shown in Table 2 below was applied by gravure coating so as to have a dry film thickness of 0.1 μm and dried to form a primer layer. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

  Next, on the primer layer side of the substrate obtained above, the cyan ink shown in Table 3 below was applied and dried so that the dry film would be 0.5 μm to form a cyan dye layer, and thermal transfer A recording medium was produced.

<Example 2>
In Example 2, a thermal transfer recording medium was prepared in the same manner as in Example 1 except that the primer layer coating solution was changed to the composition shown in Table 4 below. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

<Example 3>
In Example 3, a thermal transfer recording medium was prepared in the same manner as in Example 1 except that the primer layer coating solution was changed to the composition shown in Table 5 below. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

<Example 4>
In Example 4, a thermal transfer recording medium was prepared in the same manner as in Example 1, except that the primer layer coating solution was changed to the composition shown in Table 6 below. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

<Example 5>
In Example 5, a thermal transfer recording medium was prepared in the same manner as in Example 1, except that the primer layer coating solution was changed to the composition shown in Table 7 below. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

<Example 6>
In Example 6, a thermal transfer recording medium was prepared in the same manner as in Example 1 except that the primer layer coating solution was changed to the composition shown in Table 8 below. The fluorosurfactant contained in the primer layer is a fluorosurfactant represented by the general formula (2).

<Comparative example 1>
In Comparative Example 1, a thermal transfer recording medium was prepared in the same manner as in Example 1, except that the primer layer coating solution was changed to the composition shown in Table 9 below.

<Comparative example 2>
In Comparative Example 2, a thermal transfer recording medium was prepared in the same manner as in Example 1 except that the primer layer coating solution was changed to the composition shown in Table 10 below.

<Comparative Example 3>
In Comparative Example 3, the indaniline dye of the cyan dye layer in Example 1 was replaced with 6 parts by weight of anthraquinone dye Blue No. 403 (manufactured by Nippon Kayaku Co., Ltd.), and the primer layer coating solution was as shown in Table 11 below. A thermal transfer recording medium was prepared in the same manner except that the composition was changed to

<Comparative example 4>
In Comparative Example 4, the indaniline dye in the cyan dye layer was replaced with 6 parts by weight of the anthraquinone dye ESC451 (manufactured by Sumitomo Chemical Co., Ltd.) in Example 1, and the primer layer coating solution was as shown in Table 12 below. A thermal transfer recording medium was prepared in the same manner except for the above.

  The thermal transfer image receiving sheet was produced as follows. As a support, a coating liquid for forming an undercoat layer of the composition shown in Table 13 below is applied to a corona discharge-treated surface of 200 μm thick synthetic paper (Oji Oil Chemical Co., Ltd .: YUPO FPG # 200) having a corona discharge treatment on one side. It was applied and dried by a wire bar coating method to form an undercoat layer having a thickness of 0.5 μm.

  Subsequently, after preparing the image receiving layer formation coating liquid of the composition shown in following Table 14, it apply | coated and dried with the wire bar, the 4 micrometer-thick image receiving layer was formed, and the image receiving sheet was obtained.

  Using the thermal transfer recording media and thermal transfer image-receiving sheets of Examples 1 to 6 and Comparative Examples 1 to 4 produced as described above, evaluation of transfer density, abnormal transfer, dye crystallization, and ground fogging was performed. went. The evaluation results are shown in Table 15.

  The transfer density evaluation method was set in a sublimation thermal transfer printer (UP-CR10L; manufactured by Sony Corporation) using the thermal transfer recording media and thermal transfer image-receiving sheets of Examples 1 to 4 and Comparative Examples 1 to 4. The maximum density (cyan) of the printed portion was measured with a Macbeth densitometer RD-918 (manufactured by Sakata Inx Corporation). The thermal transfer recording medium was cut and pasted on the cyan part of the genuine medium, and printed with a cyan solid (tone value 255/255: density max) printing pattern. Printing was performed in an environment of 25 ° C. and 50%.

The evaluation of the transfer density was ranked as follows.
◎: Concentration is 2.2 or more ○: Concentration is 2.0 or more Δ: Concentration is 1.8 or more ×: Concentration is 1.6 or more XX: Concentration is less than 1.6

  In the abnormal transfer evaluation method, printing was performed under the following conditions to evaluate printing suitability. As in the case of the transfer density evaluation, a thermal transfer recording medium and an image receiving sheet are used, and the thermal transfer recording medium is cut and pasted on the cyan portion of the genuine medium and printed with a black solid print pattern (gradation value 255/255: density max). And evaluated and ranked according to the following criteria. In addition, using an unstored thermal transfer sheet and image receiving sheet, and a thermal transfer sheet and image receiving sheet stored for 2 days in an environment of 55 ° C. and 75%, printing is performed in two environments of 25 ° C., 50% environment, and 45 ° C. and 30% environment. Went.

The evaluation of abnormal transcription was ranked as follows.
A: There was no abnormal transfer under any conditions.
○: Abnormal transfer was observed only when printing at 45 ° C. and 30% with 55 ° C. and 75% storage media.
Δ: Abnormal transfer was observed either at printing at 25 ° C. and 50% with 55 ° C./75% storage media, or at 45 ° C./30% printing with non-storage media.
X: Abnormal transfer was observed both when printing at 25 ° C. and 50% with 55 ° C. and 75% storage media and when printing at 45 ° C. and 30% with non-storage media.
XX: Abnormal transfer was observed even when printing at 25 ° C. and 50% with unstored media.

  The evaluation method for dye crystallization was that the thermal transfer recording medium was stored under the following conditions to evaluate the presence or absence of dye crystallization. The cyan portion of the thermal transfer recording medium prepared by this method was stored under conditions of 70 ° C. 60% for 2 days, 55 ° C. 75% for 2 days, 45 ° C. 60% for 2 days, and 35 ° C. 80% for 2 days.

Evaluation of dye crystallization was ranked according to the following criteria.
A: Dye crystallization was not observed under any conditions.
◯: Dye crystallization was observed only when stored at 70 ° C. and 60%.
Δ: Dye crystallization was observed after storage at 70 ° C 60% and 55 ° C 75%.
X: Crystallization of the dye was observed after storage at 70 ° C 60%, 55 ° C 75%, and 45 ° C 60%.
XX: Dye crystallization was observed in any storage environment of 70 ° C. 60%, 55 ° C. 75%, 45 ° C. 60% and 35 ° C. 80%.

  The transfer density (ground fog) evaluation method was set in a sublimation thermal transfer printer (UP-CR10L; manufactured by Sony Corporation), and a Macbeth densitometer RD-918 (manufactured by Sakata Inx Corporation) with the highest density ( Cyan). The thermal transfer recording medium was cut and pasted on the cyan portion of the genuine medium, and printed with a white solid (tone value 0/255: density minimum) printing pattern. Printing was performed in an environment of 25 ° C. and 50%.

The evaluation of ground cover was ranked as follows.
◎: Concentration is 0.02 or less ○: Concentration is 0.04 or less Δ: Concentration is 0.06 or less ×: Concentration is 0.08 or less

In the ranking in each of the above evaluations, the relationship with merchantability is as follows.
◎: A level where high merchantability is recognized ○: A level acceptable as a product △: A level that is not acceptable as a product has a small margin ×: A level that is not acceptable as a product XX: A level that is not acceptable as a product

  From the results shown in Table 15, in Examples 1 to 6, the primer layer contains a fluorosurfactant, and the dye layer contains an indoaniline cyan dye represented by the general formula (1). As a result, the fluorosurfactant in the primer layer diffuses into the dye layer, and the diffused fluorosurfactant suppresses the crystallization of the dye. It turns out that became high. In Examples 1 to 6, the fluorosurfactant diffused in the dye layer improves the releasability from the image receiving sheet, suppresses abnormal transfer, and transfers the dye to a white background area where the dye is not transferred. It can be seen that so-called ground fogging can be suppressed.

  Among Examples 1 to 6, Example 4 in which the fluorosurfactant represented by the general formula (2) is contained and Example 5 in which a polyester resin is used as the primer layer resin are represented by the general formula (2). Compared to Example 6 using a fluorosurfactant different from the fluorosurfactant shown in FIG. 6 and using polyvinylpyrrolidone as the resin for the primer layer, crystallization and ground fog are further suppressed, and a better effect is obtained. You can see that

  Further, Examples 1 to 3, which contain a fluorosurfactant represented by the general formula (2) and use a polyester resin, a polyacrylic resin, and a polyurethane resin as the resin for the primer layer, are examples 4 to Compared to 6, the highest density is higher, abnormal transfer, crystallization, and fogging are further suppressed, and in almost all evaluations, it is found that high commercial properties are recognized and excellent effects are obtained.

  In contrast to these examples, Comparative Example 1 to Comparative Example 4 do not use a fluorine-based surfactant in the primer layer, use a silicon-based surfactant, or provide a primer layer. It can be seen that the holding power of the toner is weak, abnormal transfer occurs, or the maximum density is lowered. Further, in Comparative Example 3 and Comparative Example 4, since an anthraquinone dye is used as the dye, abnormal transfer occurs, the maximum density is lowered, and it can be seen that the effect cannot be obtained.

  As mentioned above, from the examples and comparative examples, the primer layer provided between the base material and the dye layer has a fluorosurfactant, particularly at least one of the fluorochemical surfactants of the general formulas (2) to (4). It can be seen that by using the cyan dye represented by the general formula (1) in the dye layer, the maximum density is high and abnormal transfer, dye crystallization, and ground fogging can be prevented.

It is sectional drawing of the thermal transfer recording medium to which this invention is applied.

Explanation of symbols

  1 thermal transfer recording medium, 2 base material, 3 primer layer, 4Y yellow dye layer, 4M magenta dye layer, 4C cyan dye layer, 5 releasable layer, 6 protective layer, 7 heat resistant slipping layer

Claims (3)

A primer layer is formed on one surface of the base material, at least one or two or more dye layers are formed on the primer layer, and a heat resistant slipping layer is formed on the other surface of the base material,
A thermal transfer recording medium, wherein the primer layer contains a fluorosurfactant, and the dye layer contains a dye selected from the following general formula (1).

(Wherein R1 and R2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; R3, R4, R5 And R6 represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or Represents an unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acylamino group, or a substituted or unsubstituted sulfonylamino group; R7 represents a hydrogen atom; and R8 represents a hydrogen atom or a substituted or unsubstituted sulfonylamino group. Represents an unsubstituted alkyl group, R9 represents a hydrogen atom or a halogen atom, and R10 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexane. Alkyl represents group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group.) 2. The thermal transfer recording medium according to claim 1, wherein the fluorosurfactant contains at least one of the following general formulas (2) to (4).
_{Rf- (L 1) m - (} Y 1) n -X ··· formula (2)
(In the general formula (2), Rf represents an aliphatic group containing at least one fluorine atom, L ₁ represents a divalent linking group, Y ₁ represents an alkyleneoxy group which may have a substituent, An alkylene group or an alkenyl group is represented, X represents a hydrogen atom, a hydroxyl group, an anionic group or a cationic group, m represents 0 or an integer of 1 to 5, and n represents 0 or an integer of 1 to 40. )
_{Rf- (O-Rf ') n1} -L 2 -X' m1 ··· general formula (3)
(In the general formula (3), Rf represents an aliphatic group containing at least one fluorine atom, Rf ′ represents an alkylene group containing at least one fluorine atom, and L ₂ represents a simple bond or linking group. X ′ represents a hydroxyl group, an anionic group, or a cationic group, and n1 and m1 each represents an integer of 1 or more.)
_{[(Rf "O) n2 - (} PFC) -CO-Y 2 ] _k -L _{3 -X" m2} ··· formula (4)
(In General Formula (4), Rf ″ represents a perfluoroalkyl group containing 1 to 4 carbon atoms, (PFC) represents a perfluorocycloalkylene group, and Y ₂ represents a linkage containing an oxygen atom or a nitrogen atom. L ₃ represents a simple bond or linking group, X ″ represents an anionic group, a cationic group, a nonionic group, or a water-solubilizing polar group containing an amphoteric group, and n2 represents 1 to 5 Represents an integer, k represents an integer of 1 to 3, and m2 represents an integer of 1 to 5.)   2. The thermal transfer recording medium according to claim 1, wherein the primer layer is mainly composed of at least one of water-soluble or water-dispersible polyester resin, polyacrylic resin, and polyurethane resin.

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