JP2009166265A - Heat transfer sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat transfer sheet featuring successful color development stability of an image before and after shelf keeping and the ability to transfer-form an image free from image nonuniformity, and a manufacturing method of the heat transfer sheet. <P>SOLUTION: This heat transfer sheet A includes a sheet-like base material 1, an undercoating layer 3 which is formed on one principal surface side of the base material 1, containing a fluorine-based surfactant, coloring material layers Y, M and C, an image protecting layer 5, etc. formed on the undercoating layer 3, as transfer layers, and a heat-resistant lubricating layer 7 which is formed on the other principal surface side of the base material 1, with the fluorine-based surfactant 9 formed on the exposed surface of the layer 7. In order to manufacture this heat transfer sheet A, first, the undercoating layer 3 containing the fluorine-based surfactant is formed on one principal surface side of the base material 1 and the heat-resistant lubricating layer 7 is formed on the other principal surface side. After these procedures, the fluorine-based surfactant 9 contained in the undercoating layer 3, is transferred to the surface of the heat-resistant lubricating layer 7 by taking up the base material 1 in the form of a roll. Finally, a transfer layer is formed on the undercoating layer 3 by paying off the base material 1 taken up in the form of a roll. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermal transfer sheet and a method for manufacturing the thermal transfer sheet, and more particularly to a thermal transfer sheet that is excellent in color stability before and after storage and that can obtain an image with reduced transfer unevenness and a method for manufacturing the thermal transfer sheet.

  As one of color or monochrome image forming techniques, there is a dye thermal transfer method. In this method, a thermal transfer sheet containing a heat diffusible dye having a property of diffusing and transferring by heating is opposed to the dye receiving layer of the image receiving sheet, and the thermal diffusion is performed on the dye receiving layer using a thermal head. An image is formed by transferring a natural dye imagewise. Such a dye thermal transfer system is well-established as a method that enables image formation using digital data, does not use a processing solution such as a developer, and can form a gradation expression comparable to a silver salt photograph.

  In such a thermal transfer system, as the transfer speed increases, problems such as an increase in applied energy due to the thermal head and an increase in frictional energy between the thermal head and the thermal transfer sheet become apparent. I have done it.

  In view of this, a configuration has been proposed in which a thermal transfer sheet having a smooth surface is obtained by adding a fluorosurfactant to the color material layer (dye layer) of the thermal transfer sheet (see Patent Document 1 below). In the thermal transfer sheet, the heat-resistant slipping layer provided on the surface that slides with the thermal head on the side opposite to the color material layer contains silicone fixed with a binder resin and a fluorine-based activator. Proposed. By adopting such a configuration, the sliding property with the thermal head is improved, and the transfer of silicone from the heat-resistant transfer layer is prevented (see Patent Document 2 below).

JP 7-101166 A Japanese Laid-Open Patent Publication No. 5-262066

  However, in the constitution in which a fluorosurfactant is added to the color material layer (dye layer), during the storage of the thermal transfer sheet, the dye is caused by the interaction between the dye coexisting in the color material layer and the fluorosurfactant. Precipitation and alteration occur, causing problems such as a decrease in printing sensitivity and a change in color tone.

  Further, in a configuration in which the heat-resistant slipping layer contains silicone fixed with a binder resin and a fluorine-based activator, the fluorine-based surfactant is adsorbed on the lubricant in the heat-resistant slipping layer. When the high-speed printing that changes from high density to low density due to the interaction between the lubricant and the fluorosurfactant, the lubricant on the back layer partially melts and accumulates heat due to the heat of the thermal head. Coloring occurs even in the portion where the thermal energy is not applied, dragged to the low gradation side, and streak-like image unevenness (so-called corduroy unevenness) generated in a corduroy shape in the printing sub-scanning direction is likely to occur. Further, it has been found that such corduroy unevenness is likely to occur particularly when a fluorosurfactant is present together with a specific melting lubricant such as a phosphate ester activator, a silicone activator, and a modified silicone resin.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal transfer sheet capable of transferring and forming an image with good color stability before and after storage and preventing image unevenness, and a method for producing the thermal transfer sheet.

  In order to achieve such an object, the thermal transfer sheet of the present invention includes a sheet-like base material, an undercoat layer containing a fluorosurfactant and provided on one main surface side of the base material, and an undercoat It is characterized by comprising a transfer layer provided on the layer and a heat-resistant slipping layer provided on the other main surface side of the substrate having a fluorosurfactant on the exposed surface.

  Moreover, this invention is also a manufacturing method of the thermal transfer sheet of such a structure, and performs the following process. First, an undercoat layer containing a fluorosurfactant is provided on one main surface side of a sheet-like substrate. Further, a heat resistant slipping layer is provided on the other main surface side of the substrate. Then, the step of transferring the fluorosurfactant contained in the undercoat layer to the surface of the heat-resistant slip layer by winding the base material provided with the undercoat layer and the heat-resistant slip layer into a roll. I do. Subsequently, the base material wound up in roll shape is unwound and the process of providing a transfer layer on the said undercoat layer is performed.

  In the thermal transfer sheet obtained as described above, it was confirmed that the color stability before and after storage was good and the occurrence of image unevenness was suppressed as described in the following examples.

  As a result of the above, according to the present invention, it is possible to obtain an image with excellent color stability even after the thermal transfer sheet is stored, and the occurrence of image unevenness such as corduroy unevenness is sufficiently suppressed. An image can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail in the order of a thermal transfer sheet, a method for manufacturing the thermal transfer sheet, and an image receiving sheet on which an image is formed by thermal transfer from the thermal transfer sheet.

≪Thermal transfer sheet≫
FIG. 1 is a schematic cross-sectional view of an essential part showing a structural example of a thermal transfer sheet A to which the present invention is applied. The thermal transfer sheet A of the embodiment shown in this figure is used for image formation by a dye thermal transfer system (sublimation thermal transfer system), and is configured as follows. That is, the thermal transfer sheet A includes an undercoat layer 3 provided on one main surface side of the sheet-like substrate 1, and each color material layer Y, M, C provided in the surface order on the undercoat layer 3, and A transfer layer such as the image protective layer 5 and a heat-resistant slip layer 7 provided on the other main surface side of the substrate 1 are further provided.

  In the drawing, the color material layers Y, M, and C serving as a transfer layer and the image protection layer 5 are provided on the primary layer 5 in the surface order. However, the thermal transfer sheet of the present invention may have a configuration in which only one color material layer or only an image protective layer is provided on the primary layer 3 as a transfer layer.

  In the thermal transfer sheet A having the above-described configuration, particularly in the present invention, the undercoat layer 3 contains a fluorosurfactant, and further, the fluorosurfactant 9 is exposed on the exposed surface of the heat resistant slipping layer 7. This fluorine-based interfacial lubricant 9 is the same as the material contained in the undercoat layer 3. Hereinafter, the detail of each layer which comprises the thermal transfer sheet A is demonstrated in order.

<Substrate 1>
The substrate 1 in the present invention is in the form of a film, and is not particularly limited to plastic film, paper, synthetic paper, cellophane, etc., and is a thin film that can withstand the heating temperature of the thermal head and can conduct heat quickly and uniformly. Those that can be produced without uneven thickness are preferred. For example, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polycarbonate, fluororesin, polymethylmeta Mention may be made of unstretched or stretched films such as acrylate, polybutene-1, polyetheretherketone, polysulfone, polyethersulfone, polyphenylene sulfide. Among these, a plastic film of polyethylene terephthalate, polyethylene naphthalate, or polyetheretherketone, which has excellent heat resistance and can be manufactured with little unevenness in thickness, is preferable.

The thickness of the substrate 1 is preferably 3.5 to 12 μm, particularly preferably 4.0 to 6.0 μm. If the substrate 1 is thin, the heat resistance of the thermal transfer sheet A is lowered. On the other hand, if the base material 1 is too thick, a step is produced in a state of being laminated on the image receiving sheet, and the color tone reproducibility is lowered due to the step, which is not preferable. The base material 1 preferably has a breaking strength of 10 to 40 kg / mm ^{2 in} both length and width and a breaking elongation of about 50 to 150% in both length and width (both according to JIS C2318). Those outside the above range may stretch or tear during winding or printing.

  In addition to providing an undercoat layer 3 and a heat-resistant slipping layer 7 described below on the surface of the base material 1, the corona discharge treatment, the prevention of foreign matter adhesion and the stability of the sheet are stabilized. Surface treatment such as antistatic treatment may be performed as necessary.

<Undercoat layer 3>
It is a layer for strengthening the adhesion of the color material layers Y, M, and C to the substrate 1 and is a layer formed using an organic material and an inorganic material, and contains a fluorine-based surfactant. Suppose that The fluorosurfactant will be described later. The undercoat layer 3 containing such a fluorosurfactant can be obtained by applying a coating solution in which a base resin and a fluorosurfactant are dissolved or dispersed.

  Examples of the base resin include polyester resins, polyacrylic ester resins, polyurethane resins, styrene acrylate resins, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and butyric acid cellulose.

  In addition to the base resin and the fluorosurfactant, the undercoat layer 3 may be, for example, silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or Hydrates, suspicious boehmite, etc.), inorganic fine particles such as aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, titanium oxide and the like. Further, for the purpose of providing the undercoat layer 3 with an improved coating solution for forming the undercoat layer 3 and an antistatic function, conventionally known cationic surfactants, anionic surfactants, etc. May be included.

<Fluorosurfactant>
Next, the fluorosurfactant contained in the undercoat layer 3 will be described. The fluorosurfactant used here is at least a compound represented by the general formulas (1) to (3).

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

In the general formula (1), 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 (1), Y ₁ represents an alkyleneoxy group or an alkylene group which may have a substituent. Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, and the like. 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 (1), 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. 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 (1), 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 (2), Rf represents an aliphatic group containing at least one fluorine atom, and the aliphatic group preferably has 1 to 18 carbon atoms, and further has 2 to 12 carbon atoms. It is preferable that it has 3 to 7 carbon atoms.

  In the general formula (2), 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 [2], 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 (2), 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 (2), n1 and m1 each independently 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 (3), 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 (3), (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 (3), 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 (3), L ₃ represents a simple bond or a linking group, and the linking group is a substituted or unsubstituted alkylene (for example, ethylene, n-propylene, or isobutylene), arylene (for example, phenylene). 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 ), generally two Valent linking group.

In the general formula (3), 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. The cationic group is preferably a quaternary alkylammonium group. The ON, halide ions, such as p- toluenesulfonic acid ion. Further, the hydroxyl group is preferably a nonionic group.

  In General Formula (3), n2 represents an integer of 1 to 5, k represents an integer of 1 to 3, m2 represents an integer of 1 to 5, n2 is preferably 3, and k is 1 or 2 is preferable, and m2 is particularly preferably 1.

  Next, although the specific example of the fluorine-type surfactant which can be used by this invention is illustrated, this invention is not limited to these.

Examples of the fluorine-based surfactant represented by the general formula (1) include the following compounds 1-1. ˜1-41 is exemplified.
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 9 F 19 -O-C 6} H 4 -SO 3 K
1-6. _{C 9 F 19 -O-C 6} H 4 -SO 3 Na
1-7. _{C 6 F 13 -O-C 6} H 4 -SO 3 K
1-8. _{C 6 F 13 -O-C 6} H 4 -SO 3 Na
1-9. C ₇ F ₁₅ COONH ₄
1-10. NaO ₃ S (CH (CHCOOCH ₂ CH ₂ C ₈ F ₁₇ ) COOCH ₂ CH ₂ C ₈ F ₁₇ )
1-11. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ COOK)
1-12. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 OPO 3 Na 2)
1-13. C ₈ F ₁₇ SO ₂ N (C ₁₂ H ₂₅ ) ((C ₂ H ₄ O) ₄ C ₄ H ₈ SO ₃ Na)
1-14. C ₆ F ₁₃ CH ₂ CH ₂ SO ₃ NH ₄
1-15. CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ SO ₃ NH ₄
1-16. CF ₃ CF ₂ (CF ₂ CF ₂ ) ₄ CH ₂ CH ₂ SO ₃ NH ₄
1-17. _{C 6 F 13 CH 2 CH 2} O-PO (ONH 4) 2
1-18. _{C 6 F 3 CH 2 CH 2} O-PO (ONH 4) (OCH 2 CH 2 OH)
1-19. C ₂ F ₅ (CH ₂ ) ₆ SO ₃ NH ₄
1-20. C ₃ F ₇ (CH ₂ ) ₅ SO ₃ NH ₄
1-21. C ₂ F ₅ (CH ₂ ) ₆ COOLi
1-22. _{C 3 F 7 (CH 2)} 3 O-C 6 H 4 -SO 3 K
1-23. NaO ₃ S (CH (CHCOO (CH ₂ ) ₉ C ₃ F ₇ ) COO (CH ₂ ) ₉ C ₃ F ₇ )
1-24. _{C 3 F 7 (CH 2)} 5 SO 2 N (C 3 H 7) (CH 2 COOK)
_{1-25.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)
1-26. (C ₂ F ₅ CH ₂ O) ₂ PO (OH) ₂
1-27. _{C 3 F 7 CH 2 CH 2} OPO (OH) 2
1-28. C ₃ F ₇ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi
1-29. C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi
1-30. (C ₆ F ₁₃ CH ₂ CH ₂ O) ₂ PO (OH) ₂
1-31. _{C 6 F 13 CH 2 CH 2} O- (CH 2 CH 2 O) 10 -H
1-32. _{C 8 F 17 CH 2 CH 2} O- (CH 2 CH 2 O) 12 -H
1-33. _{C 10 F 21 CH 2 CH 2} O- (CH 2 CH 2 O) 8 -H
1-34. _{C 4 F 9 CH 2 CH 2} O- (CH 2 CH 2 O) 20 -H
1-35. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 10 -H
1-36. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 12 -H
1-37. _{C 2 F 5 CH 2 CH 2} O- (CH 2 CH 2 O) 15 -H
1-38. _{C 3 F 7 - (CH 2} CH 2 O) 2 - (CH 2 C (OH) H-CH 2 O) 10 -H
1-39. _{C 4 F 9 -CH (CH 3} ) CH 2 O- (CH 2 CH 2 O) 9 -H
1-40. _{C 6 F 13 - (CH 2} CH 2 O) 3 - (CH 2 C (OH) H-CH 2 O) 12 -H
1-41. _{C 3 F 7 CH 2 CH 2} O- (CH 2 CH 2 O) 31 -H

Example of fluorinated surfactant represented by general formula (2) 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. HC 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

  With respect to the method for synthesizing the compound represented by the general formula (2), JP-T-10-500950 and JP-A-11-50436 can be referred to.

Example of fluorinated surfactant represented by general formula (3) 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, (PFC) represents a perfluorocyclohexylene group. The substitution position of (CF ₃ O) with respect to the perfluorocyclohexylene group is the 3,4th and 5th positions in the case of (CF ₃ O) _{3 with} the carbonyl group being in the 1st position, and the (CF ₃ O) ₂ In the case of 3rd and 4th, the case of (CF ₃ O) is in the 4th position.

  Regarding the synthesis method of the compound represented by the general formula (3), JP-A No. 10-158218 and JP-T 2000-505803 can be referred to.

  In the present invention, a fluorosurfactant having a sulfobetaine structure is preferable, and about 0.01% to 3% in the solid content of the heat resistant slipping layer is preferable.

<Heat resistant slip layer 7>
The heat resistant slipping layer 7 is provided for the purpose of preventing thermal fusion between a heating device such as a thermal head and the thermal transfer sheet A, smoothly running the thermal head, and removing deposits on the thermal head. . Such a heat-resistant slipping layer 7 is composed of a heat-resistant resin, and is characterized in that the fluorosurfactant contained in the primary layer 3 described above is adsorbed on the exposed surface side of the element. is there.

  Examples of the resin constituting the refractory slipping layer 7 include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, and nitrocellulose, polyvinyl alcohol, polyvinyl acetate, and polyvinyl. Vinyl resins such as butyral, polyvinyl acetal, and polyvinyl pyrrolidone; acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, and acrylonitrile styrene copolymer; polyimide resins, polyamide resins, polyamideimide resins, and polyvinyltoluene resins , Natural or synthetic resins such as coumarone indene resin, polyester resin, polyurethane resin, silicone-modified or fluorine-modified urethane, or a mixture 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

  Furthermore, in order to impart slidability with the thermal head, the heat-resistant slip layer 7 may be provided with heat-resistant slip by adding a solid or liquid release agent or lubricant. 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 as described above can be about 0.1 to 10 μm, preferably about 0.3 to 5 μm.

<Each color material layer Y, M, C (transfer layer)>
The color material layers Y, M, and C are applied to the undercoat layer 3 with a color material layer forming coating solution that is a heat transferable color material and has a sublimation dye, a binder resin, and a solvent. A layer formed by printing and drying.

  Of these, the dye may be a material used for a heat transfer sheet of a conventionally known thermal sublimation transfer method. Examples of such dyes include azo dyes, azomethine dyes, methine dyes, anthraquinone dyes, quinophthalone dyes, naphthoquinone dyes, and the like, and are not particularly limited. Specifically, as yellow pigments to be contained in the color material layer Y, Holon Brilliant Yellow 6GL (trade name, manufactured by Sand Corp.), PTY-52 (trade name, manufactured by Bayer), Macrolex Yellow 6G (product manufactured by Bayer) Name). As red pigments to be included in the color material layer M, MS Red G (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.), Macrolex Red Violet R (trade name, manufactured by Bayer), Selethread 7B (trade name, manufactured by Bayer) ), Samaron Red HBSL (trade name, manufactured by Hoechst), SK Rubin SEGL (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and the like. Examples of blue pigments contained in the colorant layer C include Kayaset Blue 714 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Waxoline Blue AP-FW (trade name, manufactured by Imperial Chemistry), and Holon Brilliant Blue SR (Clariant). Product name), MS Blue 100 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.), Daito Blue No. 1 (trade name, manufactured by Daitokemix Co., Ltd.).

  Moreover, binder resin may be binder resin used for a conventionally well-known thermal transfer sheet. Examples of such binder resins include cellulose resins such as cellulose addition compounds, cellulose esters, and cellulose ethers, polyvinyl acetal resins such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, and polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl acetate, Polyacetic acid-polyvinyl chloride copolymer, polyacrylamide, styrene resin, poly (meth) acrylic acid ester, poly (meth) acrylic acid, (meth) acrylic acid copolymer vinyl resin, rubber resin , Ionomer resins, olefin resins, polyester resins, and the like. Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resin having excellent storage stability is preferable.

  Moreover, the binder resin of the color material layers T, M, and C is illustrated.

  A reaction product of 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 is used. The isocyanates are diisocyanates or triisocyanates. Moreover, isocyanate is the quantity of 10-200 mass parts with respect to 100 mass parts of compounds which have active hydrogen.

  Organic solvent-soluble polymers, natural and / or semi-synthetic water-soluble polymers obtained by esterifying and / or urinating the intramolecular hydroxyl groups of natural and / or semi-synthetic water-soluble polymers.

  A cellulose acetate having a degree of acetylation of 2.4 or more and a total degree of substitution of 2.7 or more as described in JP-A-3-264393.

  Vinyl resins such as polyvinyl alcohol (Tg = 85 ° C.), polyvinyl acetate (Tg = 32 ° C.), and vinyl chloride / vinyl acetate copolymer (Tg = 77 ° C.). Polyvinyl acetal resins such as polyvinyl butyral (Tg = 84 ° C.) and polyvinyl acetoacetal (Tg = 110 ° C.). Vinyl resins such as polyacrylamide (Tg = 165 ° C.). Polyester resin such as aliphatic polyester (Tg = 130 ° C.).

  A reaction product of isocyanates described in JP-A-7-52564 and polyvinyl butyral in which the mass of the vinyl alcohol moiety contained is 15 to 40%. The isocyanates are diisocyanates or triisocyanates.

  Phenyl isocyanate-modified polyvinyl acetal resin 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 reaction Hardened | cured material of the composition containing 1 type chosen from a reactive phenoxy resin and an isocyanate reactive styrene resin, and a polyisocyanate compound.

  Polyvinyl butyral resin, preferably having a molecular weight of 60,000 or more, a glass transition temperature of 60 ° C. or more, more preferably 70 ° C. or more and 110 ° C. or less, and a mass% of the vinyl alcohol portion of 10 to 40% in the polyvinyl butyral resin, preferably Is 15-30%.

  Acrylic-modified cellulose resin, and as the cellulose resin, cellulose resins (preferably ethyl cellulose) such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and cellulose butylacetate are used. Can do.

  One of the various binder resins exemplified above can be used alone, or two or more of them can be used in combination.

<Image protection layer 5 (transfer layer)>
The image protective layer 5 is a layer that covers the surface of the image formed by thermal transfer of the color material layer on the image receiving sheet, and has at least a transparent resin layer that serves as a protective layer, and has a laminated structure as necessary. ing. As an example, the image protective layer 5 may have a configuration in which a release layer, a protective layer, and an adhesive layer are laminated in order from the primary layer 3 side. The configuration of each layer will be described in order from the primary layer 3 side.

  The release layer is a layer for securing the releasability of the image protective layer 5 from the primary layer 3, and when the releasability between the primary layer 3 and the protective layer is not appropriate, the primary layer 3 and the protective layer. It is provided to adjust the adhesion between the two. Such a release layer facilitates release between the primary layer 3 and the release layer or between the release layer and the protective layer. Such release layers include, for example, various waxes such as silicone wax, silicone resin, fluororesin, acrylic resin, water-soluble resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acrylic vinyl ether resin, anhydrous It is composed of various resins such as maleic resin and mixtures thereof.

  The protective layer is a main layer constituting the image protective layer 5, and includes, for example, a polyester resin, a polystyrene resin, an acrylic resin, a polyurethane resin, an acrylic urethane resin, a polycarbonate resin, an epoxy-modified resin of each of these resins, Examples thereof include resins obtained by modifying the resin with silicone, mixtures of these resins, ionizing radiation curable resins, ultraviolet blocking resins, and the like. Preferred resins include polyester resins, polystyrene, acrylic resins, polycarbonate resins, and epoxy-modified resins.

  The adhesive layer plays a role of adhering the image protection layer 5 to the image receiving sheet. As the resin constituting the adhesive layer, any resin containing a conventionally known pressure-sensitive adhesive, heat-sensitive adhesive or the like can be used, but a thermoplastic resin having a glass transition temperature (Tg) of 30 to 80 ° C. Is preferred. 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 image protective layer 5 can also be added with a light-proofing agent such as wax or UV (ultraviolet) absorber as an appropriate additive in the other layers of the adhesive. 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 altering or decomposing the dye, such as light energy, thermal energy, and oxidizing action.

  Among these, for example, 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 Examples thereof include wax, shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide.

  Examples of UV absorbers that serve as light-proofing agents include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based UV absorbers, such as specifically Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 312, Tinuvin 315 (manufactured by Ciba Geigy), Sumisorb-110, Sumisorb-130, Sumisorb-140, Sumisorb-200, Sumisorb-250, Sumisorb-300, 320 Sumisorb-350, Sumisorb-400 (above, manufactured by Sumitomo Chemical Co., Ltd.), Mark LA-32, M rk 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.

  As the UV absorber, a random copolymer having a Tg of 60 ° C. or higher, preferably 80 ° C. or higher, in which a reactive UV absorber and an acrylic monomer are randomly copolymerized can be used. The above-mentioned reactive UV absorbers are conventionally known salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, nickel chelate-based, hindered amine-based non-reactive UV collectors, 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 UV absorber in the random copolymer of the reactive UV absorber and the acrylic monomer as described above is in the range of 10 to 90% by mass, preferably 30 to 70% by mass. Moreover, the molecular weight of such a random copolymer can be about 5000-250,000, Preferably it can be about 9000-30000. The UV absorber described above and the random copolymer of the reactive UV absorber and the acrylic monomer may be contained alone or in combination. The addition amount of the random copolymer of the reactive UV absorber and the acrylic monomer is preferably 5 to 50% by mass with respect to the layer to be contained.

  In addition to the above UV absorbers, other light-proofing agents may be included. Specific examples of such a light-proofing agent include antioxidants and light stabilizers that are conventionally known as additives for synthetic resins, in addition to the above-described UV inhibitors. Also in that case, it may be contained in at least one layer of the heat transferable protective layer, that is, at least one of the release layer, the transparent resin layer, and the heat-sensitive adhesive layer, but is particularly preferably contained in the heat-sensitive adhesive layer.

  Examples of the antioxidant include primary antioxidants such as phenols, monophenols, bisphenols, and amines, and 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 UV 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 a ratio of 3-10 mass parts Used in. If the amount used is too small, it is difficult to obtain an effect as a light-proofing agent, while if too large, it is 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.

≪Method for manufacturing thermal transfer sheet≫
FIG. 2 is a schematic diagram for explaining a method for manufacturing the thermal transfer sheet having the above-described configuration. Next, a method for manufacturing a thermal transfer sheet will be described with reference to this figure.

  First, the heat-resistant slip layer 7 is formed on one surface of the sheet-like substrate 1 unwound from the roll shape by coating film formation. Next, the undercoat layer 3 containing a fluorosurfactant is formed on the other surface of the substrate 1 by coating. The heat resistant slipping layer 7 and the undercoat layer 3 may be simultaneously formed on both surfaces of the substrate 1. Further, after forming one layer, it may be wound up once in a roll shape and then unwound again to form the other layer.

  Next, after the heat-resistant slip layer 7 and the undercoat layer 3 are dried, the substrate 1 on which these layers are formed is wound into a roll. As a result, the undercoat layer 3 and the heat-resistant slip layer 7 provided on both side surfaces of the base material 1 are disposed in close contact with each other, and the fluorosurfactant contained in the undercoat layer 3 is added to the heat-resistant slip layer. 7 is transferred to the surface. As a result, the fluorosurfactant 9 is adsorbed on the surface of the heat resistant slipping layer 7.

  In addition, after winding the base material 1 in which the heat-resistant slipping layer 7 and the undercoat layer 3 are rolled up, it is preferable to hold this state for a predetermined time, and further to maintain a predetermined holding temperature. This ensures the transfer of the fluorosurfactant from the undercoat layer 3 to the surface of the heat resistant slipping layer 7. Such holding time and holding temperature may be set by, for example, experimentally deriving a suitable time and temperature depending on the material of the undercoat layer 3 and the heat resistant slipping layer 7.

  After the above, the sheet-like base material 1 provided with the heat-resistant slip layer 7 and the undercoat layer 3 is unwound from the roll shape, and the color material layer is formed on the undercoat layer 3 as shown in FIG. The transfer layers composed of Y, M, C, and the image protection layer 5 are printed and formed in a surface sequential manner, and these are sequentially dried after printing each layer to obtain the thermal transfer sheet A. When the thermal transfer sheet A is provided with only one type of transfer layer, any one of the color material layers Y, M, C and the image protection layer 5 is applied on the undercoat layer 3. The film may be formed and dried.

  In addition, a conventionally well-known method is used as a coating method of the coating film formation and printing formation of each layer. 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.

≪Image receiving sheet≫
Next, the configuration of the image receiving sheet on which an image is formed by thermal transfer from the above-described thermal transfer sheet will be described. The image receiving sheet includes a sheet base material and an image receiving layer provided on the one main surface side. An intermediate layer may be provided between the sheet substrate and the image receiving layer as necessary. Details of these configurations will be described below.

<Sheet base material>
The sheet base material has a role of holding the image receiving layer, and heat is applied at the time of thermal transfer. Therefore, it is preferable that the sheet base material has a mechanical strength that does not hinder handling even in an overheated state. The material for such a sheet base material 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 Etherimide, cellulose derivatives, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone , Polyether sulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene-ethylene, tetrafluoroethylene-hexafluoropropylene, polychlorotrifluoroethylene, films such as polyvinylidene fluoride and the like. In addition, a white opaque film formed by adding a white pigment or a filler to these synthetic resins or a foamed foam sheet can be used, and is not particularly limited. Moreover, the laminated body by the arbitrary combinations of the said base material 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.

  In order to obtain higher printing sensitivity and high image quality without density unevenness or white spots, it is preferable that a layer having fine voids is present in the sheet substrate. 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 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 brightener may be included. The layer having fine voids preferably has a thickness of 30 to 80 μm.

  The layer having fine voids can also be formed on the sheet substrate 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.

In addition, this sheet base material is provided on the side opposite to the side where the image receiving layer is provided, for the purpose of preventing curling, such as polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, polycarbonate, etc. A layer of resin or synthetic paper can be provided. 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. 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.

  As described above, when a plastic film and synthetic paper, or between them, or various types of paper and plastic film or synthetic paper are laminated, they can be bonded together by an adhesive layer.

  For the purpose of increasing the adhesive strength between the sheet base material and the image receiving layer, various primer treatments and corona discharge treatments are preferably performed on the surface of the sheet base material. Moreover, you may provide the surface layer which has a function as needed in the back surface side of a sheet | seat base material.

<Intermediate layer>
The intermediate layer provided as necessary between the sheet substrate and the image receiving layer includes an adhesive layer (undercoat layer), a barrier layer, an ultraviolet absorbing layer, a foamed layer, an antistatic layer, and the like. And any known layer can be used as necessary. Such an intermediate layer is not limited to a single layer, and may have a multilayered structure as necessary. Furthermore, it is preferable to add a white pigment such as titanium oxide to the base resin constituting the intermediate layer in order to conceal the glare and unevenness of the sheet base material, since the degree of freedom of base material selection is increased. The content of the base resin and the white pigment in such an intermediate layer is preferably 30 to 300 parts by weight of the white pigment solid content with respect to 100 parts by weight of the resin solid content. It is more preferable to use in the range of.

  Moreover, as an intermediate | middle layer, the layer which hardened the thermoplastic resin, the thermosetting resin, or the thermoplastic resin which has a functional group using various additives and 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.

<Image receiving layer>
The image receiving layer has a configuration in which various additives such as a release agent are contained as necessary together with a binder resin. A well-known thing can be used for binder resin, It is preferable to use what a dye is easy 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. can be used alone or as a mixture, Among these, polyester resins and vinyl resins are preferable.

  In such an image receiving layer, it is preferable to add a release agent in order to prevent thermal fusion with the color material layers Y, M, and C on the thermal transfer sheet A side. 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 silicones, epoxy-modified silicones, alcohol-modified silicones, vinyl-modified silicones, urethane-modified silicones, and the like can be blended or polymerized 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. When the range of the addition amount is not satisfied, problems such as fusion between the thermal transfer sheet and the image receiving layer of the image receiving sheet or a decrease in printing sensitivity may occur. These releasing agents may not be added to the image receiving layer, but may be provided separately as a releasing layer on the image receiving layer.

  The image-receiving layer having the above-described configuration is obtained by applying a coating solution in which a binder resin or an additive is dissolved or dispersed in a solvent such as water or an organic solvent on a sheet base material (intermediate layer), a bar coater, a gravure printing method, It can be formed by applying and drying by the usual methods such as screen printing, roll coating, reverse roll coating using a gravure plate, air knife coating, spray coating, curtain coating, and extrusion coating. it can. The intermediate layer and back layer forming means provided on one surface of the sheet substrate are also performed in the same manner as in the case of the image receiving layer. In addition, the image receiving layer is not only formed by directly applying the coating solution on the sheet substrate and drying as described above, but also having an image receiving layer formed in advance on another support. Alternatively, the image receiving layer may be transferred and formed. 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 as described above is the thickness after coating and drying, and is preferably about 0.1 to 10 μm.

  Note that the image receiving sheet used here may be supplied to the printer as a single sheet or as a roll. The sheet supply refers to, for example, a form in which an image receiving sheet is cut into a certain size, about 50 sheets are put in a cassette and mounted on a printer. The roll form is a form in which the image-receiving sheet is supplied to the printer in that form and cut into a desired size after printing. 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, particularly when the postcard specification is as described above, or when using a label or a seal type image receiving sheet, a design mark such as a postal 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 can be provided on the back side.

  The thermal transfer sheet of each Example 1-5 and Comparative Examples 1-4 was produced in the following procedures.

Example 1
(1) First, Lumirror 6F65K (trade name, manufactured by Toray Industries, Inc.) having a thickness of 6 μm was prepared as the film-like substrate 1. The following composition <a. The coating solution for forming a heat resistant slipping layer> was applied by gravure coating and dried to form a heat resistant slipping layer 7 having a thickness of 0.5 μm. Further, on the other surface of the substrate 1, <b. Undercoat layer forming coating solution> was applied by gravure coating and dried to form an undercoat layer 3 having a thickness of 0.1 μm.

<A. Coating liquid for forming heat resistant slipping layer>
Polyvinyl butyral resin (Sekisui Chemical Co., Ltd. ESREC BX-1) 3.5 parts by weight Phosphate ester surfactant 3.0 parts by weight (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A208S)
Phosphate ester surfactant 0.3 parts by weight (Toho Chemical Co., Ltd .: Phosphanol RD720)
19.0 parts by weight of polyisocyanate (Dainippon Ink Chemical Co., Ltd .: Burnock D750-45)
Talc (Nippon Talc Co., Ltd .: Y / X = 0.03) 0.2 parts by weight Methyl ethyl ketone 35.0 parts by weight Toluene 35.0 parts by weight

<B. Undercoat layer forming coating solution>
40.0 parts by weight of polyester (Toyo Morton Co., Ltd .: Adcoat 335A)
Fluorosurfactant-1 (manufactured by 3M: Novec FC-4430) 0.02 parts by weight Methyl ethyl ketone 60.0 parts by weight

(2) The substrate 1 after forming the undercoat layer 3 and the heat-resistant slipping layer 7 was wound into a roll and stored for 5 days in an environment of 30 ° C. ± 15 ° C.

(3) The substrate 1 stored in a roll shape is unwound, and the following composition <c1. -C3. Coloring agent forming coating liquid> and <d1. -D3. An image protective layer forming coating solution> was formed in the surface order by gravure coating and dried to form each color material layer Y, M, C having a film thickness of 0.5 μm and the image protective layer 5. The image protective layer 5 has a structure in which three layers of a peeling layer, a protective layer, and an adhesive layer are laminated in order from the side closer to the undercoat layer 3 <d1. -D3. The coating solution for forming an image protective layer> was sequentially printed on the same surface. The film thickness of these three layers was set so that the release layer was 0.3 μm, the protective layer was 0.8 μm, and the adhesive layer was 0.5 μm in order from the lower layer.

<C1. Yellow Color Material Layer Forming Coating Solution>
Holon Brilliant Yellow S.6GL 3.0 parts by weight
(Yellow dye Sand Co., Ltd. product name)
ESREC KS-5 4.0 parts by weight (Acetacetal Sekisui Chemical Co., Ltd., trade name)
0.5 parts by weight of melamine / formaldehyde condensate fine particles
Methyl ethyl ketone 50.0 parts by weight Toluene 43.0 parts by weight

<C2. Colorant layer forming coating solution for magenta>
The composition was the same except that the yellow dye was replaced with 2 parts by weight of MS Red G (magenta dye, trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.) in the yellow colorant layer forming coating solution.

<C3. Cyan colorant layer forming coating solution>
The composition was the same except that the yellow dye was replaced with 4 parts by weight of DH.C2 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in the yellow colorant layer forming coating solution.

<D1. Image protection layer forming coating solution (release layer)>
Polyvinyl acetoacetal (Sekisui Chemical's ESREC KS-5) 5 parts Methyl ethyl ketone 55 parts Toluene 40 parts

<D2. Image protective layer coating liquid (protective layer)>
20 parts of acrylonitrile styrene resin (Lightac A, manufactured by Nippon A & L Co., Ltd.)
UV-absorbing resin (UVA635L manufactured by BSAF) 2 parts Methyl ethyl ketone 40 parts Toluene 38 parts

<D3. Image protection layer forming coating solution (adhesive layer)>
Acrylic resin (Mitsubishi Rayon, Dianar BR90) 6 parts Hydrogenated petroleum resin (Arakawa Chemical Industries, Alcon P100) 1 part

<< Example 2 >>
In the procedure of Example 1, <b. The thermal transfer sheet A was prepared in the same manner as in Example 1 except that the fluorosurfactant in the undercoat layer forming coating liquid> was replaced by fluorosurfactant-2 (manufactured by Neos: Footgent 100C). Produced. In addition, fluorine-type surfactant-2 is a compound shown by the general formula (1) mentioned above.

Example 3
In the procedure of Example 1, <a. The polyvinyl butyral resin used in the coating solution for forming a heat resistant slipping layer (S-LEC BX-1 manufactured by Sekisui Chemical Co., Ltd.) was changed to a silicone-modified butyral resin (X41-1222 manufactured by Shin-Etsu Chemical Co., Ltd.). b. A thermal transfer sheet A was prepared in the same manner as in Example 1 except that the fluorosurfactant in the undercoat layer forming coating liquid> was replaced with fluorosurfactant-3 (Neto's Footgent 150). did. In addition, fluorine-type surfactant-3 is a compound shown by the general formula (1) mentioned above.

Example 4
In the procedure of Example 3, <b. The thermal transfer sheet A was prepared in the same manner as in Example 3 except that the fluorosurfactant in the undercoat layer-forming coating liquid> was replaced with fluorosurfactant-4 (manufactured by Neos: Aftergent 400SW). Produced. In addition, fluorine-type surfactant-4 is a compound shown by the general formula (2) mentioned above.

Example 5
In the procedure of Example 1, <b. A thermal transfer sheet A was prepared in the same manner as in Example 1 except that the fluorosurfactant in the undercoat layer-forming coating liquid> was replaced with fluorosurfactant-5 (manufactured by DuPont: Zonyl FS). did. In addition, fluorine-type surfactant-5 is a compound shown by the general formula (3) mentioned above.

≪Comparative example 1≫
In the procedure of Example 1, the base material on which the heat resistant slipping layer was formed was once wound up in a roll shape and stored for 5 days in an environment of 30 ° C. ± 15 ° C. Thereafter, the undercoat layer, each color material layer, and image protection A transfer layer such as a layer was applied and formed at the same time, and then wound into a roll to produce a thermal transfer sheet.

≪Comparative example 2≫
In the procedure of Comparative Example 1, a transfer layer such as each color material layer and an image protective layer was applied and formed while performing corona treatment instead of forming the undercoat layer, and a thermal transfer sheet was produced.

«Comparative Example 3»
In the procedure of Example 1, <b. A transfer sheet was prepared in the same manner as in Example 1 except that a nonionic surfactant (Olfin E1010: manufactured by Nissin Chemical Co., Ltd.) was used instead of the fluorosurfactant in the undercoat layer forming coating liquid>. did.

<< Comparative Example 4 >>
In the procedure of Example 1, <b. Except that the fluorosurfactant was not added to the coating liquid for forming the undercoat layer, and that the fluorosurfactant-1 was introduced into the coating liquid for the transfer layer such as each color material layer and the image protective layer. A transfer sheet was prepared in the same manner as in Example 1.

<< Production of image receiving sheet >>
The image receiving sheet used for the evaluation of the thermal transfer sheet package obtained as described above was prepared as follows.

(1) As a sheet substrate, a 200 μm-thick synthetic paper (manufactured by Oji Yuka: YUPO FPG # 200) with one side subjected to corona discharge treatment was facilitated. On the surface of the sheet base material subjected to the corona discharge treatment, an undercoat layer serving as an intermediate layer has the following composition <e. The undercoat layer forming coating solution> was applied and dried by a wire bar coating method to form an undercoat layer having a thickness of 0.5 μm.

<E. Undercoat layer forming coating solution>
Polyvinyl butyral [manufactured by Sekisui Chemical: Eslex BL-1] 9 parts isocyanate [manufactured by Nippon Polyurethane: Coronate HX] 1 part methyl ethyl ketone 80 parts butyl acetate 10 parts

(2) Next, <f. After preparing the image receiving layer forming coating solution, it was coated and dried with a wire bar to form an image receiving layer having a thickness of 4 μm, thereby obtaining an image receiving sheet.

<F. Image-receiving layer forming coating solution>
Polyvinyl butyral resin 6.0 parts [Sekisui Chemical Co., Ltd .: Eslex BX-1, butyral degree of 70 mol%, unsaponified vinyl acetate group 3 mol%]
Silicone modified butyral resin (Shin-Etsu Chemical Co., Ltd .: X41-1222) 1.0 part isocyanate [Nippon Polyurethane: Coronate 3041] 0.5 part

≪Image formation using thermal transfer sheet≫
The produced thermal transfer sheets of Examples 1 to 5 and Comparative Examples 1 to 4 were stored under predetermined storage conditions, and image formation was performed using the thermal transfer sheets before and after storage. The thermal transfer sheet was stored for one week in a temperature environment of 50 ° C. For image formation, a sublimation thermal transfer printer (UP-CR10L; manufactured by Sony Corporation) was used to transfer the transfer layer (each color material layer and image protective layer) from the thermal transfer sheet to the image receiving layer of the image receiving sheet to form an image.

≪Evaluation of thermal transfer sheet packaging≫
The following measurements were performed on the images formed as described above.

(A) Change in optical density of image formed using thermal transfer sheet before and after storage [ΔO. D. ] And color difference change [ΔE]. Here, for the portions where the optical density (OD value) of K (process black) is 1.0 and 0.5, the O.D. The D value and the color difference were measured with an X-rite 810 densitometer (manufactured by X-Rite), and the change in optical density before and after storage [ΔO. D. ] And formula difference change [ΔE (ΔEa * b *)].
ΔO. D. = (OD value before storage)-(OD value after storage)
ΔE (ΔEa * b *) = [(a * value before storage−a * value after storage) ² + (b * value before storage−b * value after storage) ² ] ^1/2

As an evaluation standard for the obtained value, optical density change [ΔO. D. ] Is ± 0.04 or more, and the formula difference change [ΔE] is 3 or more, it is an unacceptable level as a product. These values are shown as follows.
A: [ΔO. D. ] 0.02 or less [ΔE] 2 or less ○: [ΔO. D. ] 0.03 or less [ΔE] 2.5 or less Δ: [ΔO. D. ] 0.04 or less [ΔE] Less than 3 ×: [ΔO. D. ] 0.05 or less [ΔE] 3 or more XX: [ΔO. D. ] 0.06 or less [ΔE] 4 or more

(B) Regarding image density unevenness (corduroy unevenness), unevenness in an image was evaluated in a gradation image changing from the highest neutral density to the lowest density from the start to the end of image printing. The criteria for evaluation are as follows.
A: Unevenness is not seen at all.
○: Some corduroy unevenness is observed at the upper end of the image, but there is no fading as the image Δ: Some unevenness is observed in the image ×: Corduroy unevenness is widely observed in the intermediate gradation area in the image XX : Corduroy-like unevenness is observed throughout the image.

  The evaluation results of (a) and (b) above are shown in Table 1 below. Table 1 below also shows the features related to the manufacture of Examples 1 to 5 and Comparative Examples 1 to 4.

  As shown in Table 1, the image formed using the thermal transfer sheet produced by the procedure applying the production method of the present invention has an optical density change [ΔO. D. ] And the color difference change [ΔE] are within an allowable range, it is confirmed that the color development stability of the image is good, and corduroy generation (image density unevenness generation) is also prevented.

  On the other hand, an image formed using a thermal transfer sheet produced without applying the present invention has insufficient color development stability of the image, and can prevent the occurrence of corduroy (occurrence of unevenness of image density). I found out.

  From the above, the thermal transfer sheet obtained by applying the present invention is excellent in color stability by thermal transfer from the thermal transfer sheet even after storage, and sufficiently suppresses the occurrence of image irregularities such as corduroy irregularities. It was confirmed that the obtained image could be obtained.

It is a principal part cross-sectional schematic diagram which shows the structure of the thermal transfer sheet of embodiment. It is a schematic diagram explaining the manufacturing method of the thermal transfer sheet of embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Base material, 3 ... Undercoat layer, 5 ... Image protective layer (transfer layer), 7 ... Heat-resistant slip layer, 9 ... Fluorine-type interface slip agent, A ... Thermal transfer sheet, Y ... Color material layer for yellow color (Transfer layer), M: magenta color material layer (transfer layer), C: cyan color material layer (transfer layer)

Claims (5)

A sheet-like substrate;
An undercoat layer containing a fluorosurfactant and provided on one main surface side of the substrate;
A transfer layer provided on the undercoat layer;
A thermal transfer sheet comprising: a heat-resistant slipping layer provided on the other main surface side of the base material having the fluorosurfactant on an exposed surface. The thermal transfer sheet according to claim 1,
The thermal transfer sheet, wherein the fluorosurfactant is represented by general formulas (1) to (3).

In the general formula (1), Rf represents an aliphatic group containing at least one fluorine atom, L ₁ represents a divalent linking group, and Y ₁ represents an alkyleneoxy group or alkylene which may have a substituent. A group or an alkenyl group, 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 an integer of 0 or 1 to 40.

In the general formula (2), 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 independently represents an integer of 1 or more.

In the general formula (3), Rf ″ represents a perfluoroalkyl group containing 1 to 4 carbon atoms, (PFC) represents a perfluorocycloalkylene group, and Y ₂ represents a linking group containing an oxygen atom or a nitrogen atom. L ₃ represents a simple bond or linking group, X ″ represents a water-solubilizing polar group containing an anionic group, a cationic group, a nonionic group, or an amphoteric group, and n2 is an integer of 1 to 5 K represents an integer of 1 to 3, and m2 represents an integer of 1 to 5. The thermal transfer sheet according to claim 1,
The thermal transfer sheet, wherein the heat-resistant slipping layer contains at least one of a phosphoric ester surfactant, a silicon surfactant, and a modified silicone resin. Providing a subbing layer containing a fluorosurfactant on one main surface side of the sheet-like substrate;
Providing a heat-resistant slipping layer on the other principal surface side of the substrate;
A step of transferring the fluorosurfactant contained in the undercoat layer to the surface of the heat-resistant slip layer by winding the base material provided with the undercoat layer and the heat-resistant slip layer into a roll shape; ,
A method of producing a thermal transfer sheet, comprising: unwinding the base material wound up in the roll shape and providing a transfer layer on the undercoat layer. In the manufacturing method of the thermal transfer sheet of Claim 4,
A method for producing a thermal transfer sheet, wherein the base material is wound in a roll shape for a predetermined time.

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