JP2001010236A - Thermal recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the preservation safety of an uncolored part and a colored image and to secure touch close to the feeling of plain paper by using a color developer composition containing compounds expressed by specified formulas respectively as the electron accepting compound of a thermal recording layer formed on a support. SOLUTION: In a thermal recording material in which a thermal recording layer containing an electron donative compound and an electron accepting compound is formed on a support, and a protective layer is formed on the thermal recording layer, a color developer composition containing at least one compound selected from compounds expressed by formula I and at least one compound selected from compounds expressed by formulas II, III is used as an electron accepting compound. In the formulas, X1-X3 are each hydrogen, halogen, alkyl, or the like; Z1-Z3 are each hydrogen, or alkyl; R1-R5, R11-R15, R21-R25, R31-R35 are each hydrogen, halogen, alkyl, or the like, and these can form a carbon cyclic aromatic ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a heat-sensitive recording material. More specifically, the present invention relates to a heat-sensitive recording material in which the storage stability of an uncolored portion and a color image is improved. Further, the present invention relates to a heat-sensitive recording material having a feel similar to that of plain paper.

[0002]

2. Description of the Related Art Hitherto, heat-sensitive recording materials utilizing a color reaction between an electron-donating color-forming compound and an electron-accepting compound (a color developer) are well known (for example, Japanese Patent Publication No. Sho 43-4).
No. 160, JP-B-45-14039). Thermosensitive recording materials are relatively inexpensive, and have the advantage that their recording equipment is compact and maintenance-free, and are widely used in the fields of facsimile machines, recorders, and printers. Recently, the field of application of heat-sensitive recording materials has been further expanded and diversified, and further expanded to applications under severe environments (for example, labels, prepaid cards, etc.). However, heat-sensitive recording materials using electron-accepting compounds such as 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"] and benzyl 4-hydroxybenzoate, which are conventionally known, cannot be used in severe environments. (For example, under contact with writing instruments such as oil, solvents, oils and fats, and a highlighter, or in a humid environment), the uncolored portion is significantly contaminated (ground stain), and the color image is faded. There are drawbacks.

For the purpose of remedying such a drawback, a heat-sensitive recording material (heat-sensitive recording material) using an N- (hydroxyphenyl) -benzenesulfonamide derivative as an electron-accepting compound has been proposed (for example, Japanese Patent Publication No. Hei 5 (1994)). −13071
No.).

However, this heat-sensitive recording material also has poor storage stability of a color image, and further improvement is required at present when a high-performance heat-sensitive recording material is required.

In order to improve such disadvantages, for example,
A heat-sensitive recording material in which a protective layer (an overcoat layer, an intermediate layer and an overcoat layer, etc.) is provided on a heat-sensitive recording layer is known (for example, JP-A-1-255588, JP-A-6-255).
2-279980). Although the storage stability of the uncolored portion and the color image is improved by such a method, it cannot be said that it still has sufficient performance.

Further, since the heat-sensitive recording material has a very high level of smoothness on the surface of the recording layer, it is extremely glossy as compared with plain paper for general office use, and has an uncomfortable touch or discomfort. is there. Furthermore, a writing instrument such as a pencil has a drawback that it is difficult to write on the surface of the heat-sensitive recording material.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording material having improved storage stability of uncolored areas and color-formed images, and a heat-sensitive recording material whose feel is close to that of plain paper. It is also to provide a recording material.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to meet the above-mentioned demands, and as a result, have completed the present invention.

That is, the present invention provides: 1) a heat-sensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound on a support, and a protective layer provided on the heat-sensitive recording layer. In the recording material, as the electron-accepting compound, at least one selected from the compounds represented by the general formula (1) and at least one selected from the compounds represented by the general formulas (2) and (3) Heat-sensitive recording material using a developer composition containing a kind of compound,

Embedded image (Wherein X ₁ , X ₂ and X ₃ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group,
Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom or an alkyl group, and R _{1 to} R ₅ , R _{11 to} R ₁₅ , R _{21 to} R ₂₅ and R _{31 to} R
₃₅ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and further, R ₁ and R ₂ , R ₂
And R ₃ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ , R ₃₁ and R ₃₂ , or R ₃₂ and R ₃₃ , the mutually adjacent groups are bonded to each other To form a carbocyclic aromatic ring together with the carbon atom which is substituted) 2) 100 parts by weight of the compound represented by the general formula (1) At least one compound selected from the compounds represented by the formula (3) is used in an amount of 0.01 to 10;
3) The heat-sensitive recording material according to 1) or 2) further containing a heat-fusible compound in the heat-sensitive recording layer. 4) The ultraviolet light absorption in the heat-sensitive recording layer. 5) The heat-sensitive recording material according to any one of 1) to 3) above, wherein the heat-sensitive recording layer further contains a hindered phenol compound. 6) The heat-sensitive recording material according to any one of 1) to 5), further comprising a binder in the heat-sensitive recording layer; 7) The heat-sensitive recording layer further containing a pigment in the heat-sensitive recording layer
6) The heat-sensitive recording material according to any one of 8), 8) the pigment has an oil absorption of 5 according to JIS K-5101 method.
9) The heat-sensitive recording material according to 7), which is 0 ml / 100 g or more; 9) The heat-sensitive recording material according to any one of 1) to 8) above, further comprising an undercoat layer provided between the support and the heat-sensitive recording layer. 10) The heat-sensitive recording material according to any one of 1) to 9), wherein the protective layer comprises an overcoat layer containing a water-soluble resin or a water-dispersible resin and a pigment as main components. The above 1) to 1 containing an ultraviolet absorber
0) The thermosensitive recording material according to any one of the above, 12) The ultraviolet absorbent is encapsulated in microcapsules, the thermosensitive recording material according to 11), 13) The water-soluble resin or the water-dispersible resin is formed into a film. The thermosensitive recording material according to any one of the above 10) to 12), which is a resin having a tear strength of 1 kg / mm or more at 20 ° C. and 60% relative humidity (RH). 14) The protective layer is made of a water-soluble resin. Or 1) to 13) above, comprising an intermediate layer mainly composed of a water-dispersible resin and an overcoat layer mainly composed of an ionizing radiation-curable resin.
Any of the heat-sensitive recording materials described above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The heat-sensitive recording material of the present invention is a heat-sensitive recording material in which a heat-sensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound is provided on a support, and a protective layer is further provided on the heat-sensitive recording layer. And, as the electron accepting compound, at least one compound selected from the compounds represented by the general formula (1) and at least one compound selected from the compounds represented by the general formulas (2) and (3) Is used.

Embedded image (Wherein X ₁ , X ₂ and X ₃ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group,
Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom or an alkyl group, and R _{1 to} R ₅ , R _{11 to} R ₁₅ , R _{21 to} R ₂₅ and R _{31 to} R
₃₅ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and further, R ₁ and R ₂ , R ₂
And R ₃ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ , R ₃₁ and R ₃₂ , or R ₃₂ and R ₃₃ , the mutually adjacent groups are bonded to each other And may form a carbocyclic aromatic ring together with the carbon atoms that are substituted)

Formula (1), Formula (2), Formula
In the compound represented by (3), X ₁, X _TwoAnd X _Three
Is hydrogen atom, halogen atom, alkyl group, alkoxy
Or a hydroxyl group, preferably a hydrogen atom, a halo
Gen atom (for example, fluorine atom, chlorine atom, bromine atom
), An alkyl group having 1 to 6 carbon atoms (for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, tert-butyl group, n-pliers
Group, n-hexyl group, cyclopentyl group, cyclohexyl
A sil group), an alkoxy group having 1 to 6 carbon atoms (for example,
Xy, ethoxy, n-propoxy, n-butoxy
Group, isobutoxy group, n-pentyloxy group, n-hexyl
Siloxy group, cyclohexyloxy group), hydroxyl group
More preferably a hydrogen atom, a halogen atom, or
An alkyl group having 1 to 4 carbon atoms, more preferably
It is a hydrogen atom or a halogen atom.

Formula (1), Formula (2), Formula
In the compound represented by (3), Z ₁, Z _TwoAnd Z _Three
Represents a hydrogen atom or an alkyl group, preferably water
An atom atom, an alkyl group having 1 to 6 carbon atoms (for example, methyl
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, tert-butyl group, n-pe
Methyl, n-hexyl, cyclopentyl, cyclo
Hexyl group), more preferably, a hydrogen atom, or
It is an alkyl group having 1 to 4 carbon atoms.

Formula (1), Formula (2), Formula
In the compound represented by (3), R ₁~ R _Five, R ₁₁~ R
_Fifteen, R _{twenty one}~ R _{twenty five}And R ₃₁~ R ₃₅Is hydrogen atom, halogen
Atom, alkyl group, alkoxy group, or aryl group
And preferably represents a hydrogen atom, a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom)
Alkyl group (for example, methyl group, ethyl group, n-propyl
Group, isopropyl group, n-butyl group, isobutyl group, t
tert-butyl group, n-pentyl group, n-hexyl group,
Cyclopentyl group, cyclohexyl group), having 1 to 6 carbon atoms
Alkoxy group (for example, methoxy group, ethoxy group, n
-Propoxy group, n-butoxy group, isobutoxy group, n
-Pentyloxy group, n-hexyloxy group, cyclohexyl
Xyloxy group), aryl group having 6 to 10 carbon atoms (eg,
For example, phenyl, 4-methylphenyl, 3-methylphenyl
Phenyl, 2-methylphenyl, 4-ethylphenyl
Group, 3-ethylphenyl group, 4-n-propylphenyl
Group, 4-isopropylphenyl group, 4-n-butylphen
Nyl group, 4-sec-butylphenyl group, 4-ter
t-butylphenyl group, 4-methoxyphenyl group, 3-
Methoxyphenyl group, 2-methoxyphenyl group, 4-E
Toxiphenyl group, 4-isopropoxyphenyl group, 4
-N-butoxyphenyl group, 4-fluorophenyl group,
3-fluorophenyl group, 4-chlorophenyl group, 3-
Chlorophenyl group, 2-chlorophenyl group, 4-chloro
-2-methylphenyl group, 4-chloro-3-methylphen
Nyl group, 2,4-dimethylphenyl group, 2,5-dimethyl
Phenyl group, 3,4-dimethylphenyl group, 2,4-
Dichlorophenyl group, 2,5-dichlorophenyl group, 2
-Methoxy-4-methylphenyl group, 2-methyl-4-
Methoxyphenyl group, 2,4-dimethoxyphenyl group,
3,4-dimethoxyphenyl group, 3,5-diethoxyf
Enyl group, 1-naphthyl group, 2-naphthyl group),
More preferably, a hydrogen atom, a halogen atom, a carbon number of 1 to
An alkyl group of 4 or an alkoxy group having 1 to 4 carbon atoms
Yes, more preferably a hydrogen atom, or a carbon number of 1 to
4 alkyl group.

Further, general formulas (1), (2),
In the compound represented by the general formula (3), R ₁And R _Two, R _Two
And R _Three, R ₁₁And R ₁₂, R ₁₂And R ₁₃, R _{twenty one}And R _{twenty two}, R _{twenty two}When
R _{twenty three}, R ₃₁And R ₃₂Or R ₃₂And R ₃₃Each other selected from
Groups adjacent to each other are bonded to each other to
May form a carbocyclic aromatic ring together with
Alternatively, a benzene ring may be formed.

In the compound represented by the general formula (1),
It is a sulfonamide derivative having a phenolic hydroxyl group, and the substitution position of the hydroxyl group is 4-position, 3-position or 2-position with respect to the sulfonamide group, more preferably,
This is the fourth or third position. That is, the general formula (1)
Compounds represented by -a) or general formula (1-b) are more preferred.

Embedded image [Wherein X ₁ , Z ₁ and R _{1 to} R ₅ have the same meaning as in the general formula (1)]

Specific examples of the compound represented by the general formula (1) include, for example, the following compounds, but of course, the present invention is not limited thereto.

-Exemplified Compound No. 1-1. N- (4-hydroxyphenyl) -benzenesulfonamide 1-2. N- (4-hydroxyphenyl)-(2'-methylbenzene) sulfonamide 1-3. N- (4-hydroxyphenyl)-(3'-methylbenzene) sulfonamide 1-4. N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-5. N- (4-hydroxyphenyl)-(4'-ethylbenzene) sulfonamide 1-6. N- (4-hydroxyphenyl)-(4'-n-propylbenzene) sulfonamide 1-7. N- (4-hydroxyphenyl)-(4'-isopropylbenzene) sulfonamide 1-8. N- (4-hydroxyphenyl)-(4'-n-butylbenzene) sulfonamide 1-9. N- (4-hydroxyphenyl)-(4'-tert-butylbenzene) sulfonamide 1-10. N- (4-hydroxyphenyl)-(4'-n-pentylbenzene) sulfonamide 1-11. N- (4-hydroxyphenyl)-(4'-n-hexylbenzene) sulfonamide 1-12. N- (4-hydroxyphenyl)-(4'-cyclohexylbenzene) sulfonamide 1-13. N- (4-hydroxyphenyl)-(3 ', 4'-dimethylbenzene) sulfonamide 1-14. N- (4-hydroxyphenyl)-(3'-methoxybenzene) sulfonamide 1-15. N- (4-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-16. N- (4-hydroxyphenyl)-(4'-ethoxybenzene) sulfonamide 1-17. N- (4-hydroxyphenyl)-(4'-isopropoxybenzene) sulfonamide 1-18. N- (4-hydroxyphenyl)-(4'-n-butoxybenzene) sulfonamide 1-19. N- (4-hydroxyphenyl)-(4'-n-pentyloxybenzene) sulfonamide 1-20. N- (4-hydroxyphenyl)-(4'-n-hexyloxybenzene) sulfonamide 1-21. N- (4-hydroxyphenyl)-(3'-fluorobenzene) sulfonamide 1-22. N- (4-hydroxyphenyl)-(4'-fluorobenzene) sulfonamide 1-23. N- (4-hydroxyphenyl)-(2'-chlorobenzene) sulfonamide 1-24. N- (4-hydroxyphenyl)-(3'-chlorobenzene) sulfonamide 1-25. N- (4-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-26. N- (4-hydroxyphenyl)-(4'-phenylbenzene) sulfonamide 1-27. N- (4-hydroxyphenyl)-(1'-naphthalene) sulfonamide 1-28. N- (4-hydroxyphenyl)-(2'-naphthalene) sulfonamide 1-29. N- (2-methyl-4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-30. N- (3-methyl-4-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-31. N- (3-methoxy-4-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-32. N- (2-Chloro-4-hydroxyphenyl) -benzenesulfonamide 1-33. N- (2,4-dihydroxyphenyl) -benzenesulfonamide 1-34. N- (3,4-dihydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-35. N-methyl-N- (4-hydroxyphenyl) -benzenesulfonamide 1-36. N-methyl-N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-37. N-methyl-N- (4-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-38. N-ethyl-N- (4-hydroxyphenyl) -benzenesulfonamide 1-39. N-ethyl-N- (4-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-40. Nn-propyl-N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-41. Nn-butyl-N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-42. N-ethyl-N- (4-hydroxyphenyl)-(4'-phenylbenzene) sulfonamide 1-43. N-methyl-N- (4-hydroxyphenyl)-(1'-naphthalene) sulfonamide 1-44. N- (3-hydroxyphenyl) -benzenesulfonamide 1-45. N- (3-hydroxyphenyl)-(2'-methylbenzene) sulfonamide 1-46. N- (3-hydroxyphenyl)-(3'-methylbenzene) sulfonamide 1-47. N- (3-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-48. N- (3-hydroxyphenyl)-(4'-ethylbenzene) sulfonamide 1-49. N- (3-hydroxyphenyl)-(4'-n-propylbenzene) sulfonamide 1-50. N- (3-hydroxyphenyl)-(4'-isopropylbenzene) sulfonamide 1-51. N- (3-hydroxyphenyl)-(4'-n-butylbenzene) sulfonamide 1-52. N- (3-hydroxyphenyl)-(4'-tert-butylbenzene) sulfonamide 1-53. N- (3-hydroxyphenyl)-(4'-n-pentylbenzene) sulfonamide 1-54. N- (3-hydroxyphenyl)-(4'-n-hexylbenzene) sulfonamide 1-55. N- (3-hydroxyphenyl)-(4'-cyclohexylbenzene) sulfonamide 1-56. N- (3-hydroxyphenyl)-(3 ', 4'-dimethylbenzene) sulfonamide 1-57. N- (3-hydroxyphenyl)-(3'-methoxybenzene) sulfonamide 1-58. N- (3-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-59. N- (3-hydroxyphenyl)-(4'-ethoxybenzene) sulfonamide 1-60. N- (3-hydroxyphenyl)-(4'-isopropoxybenzene) sulfonamide 1-61. N- (3-hydroxyphenyl)-(4'-n-butoxybenzene) sulfonamide 1-62. N- (3-hydroxyphenyl)-(4'-n-pentyloxybenzene) sulfonamide 1-63. N- (3-hydroxyphenyl)-(4'-n-hexyloxybenzene) sulfonamide 1-64. N- (3-hydroxyphenyl)-(3'-fluorobenzene) sulfonamide 1-65. N- (3-hydroxyphenyl)-(4'-fluorobenzene) sulfonamide 1-66. N- (3-hydroxyphenyl)-(2'-chlorobenzene) sulfonamide 1-67. N- (3-hydroxyphenyl)-(3'-chlorobenzene) sulfonamide 1-68. N- (3-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-69. N- (3-hydroxyphenyl)-(4'-phenylbenzene) sulfonamide 1-70. N- (3-hydroxyphenyl)-(1'-naphthalene) sulfonamide 1-71. N- (3-hydroxyphenyl)-(2'-naphthalene) sulfonamide 1-72. N- (2-Methyl-3-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-73. N- (4-methyl-3-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-74. N- (5-Methyl-3-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-75. N- (4-methoxy-3-hydroxyphenyl) -benzenesulfonamide 1-76. N- (5-Chloro-3-hydroxyphenyl) -benzenesulfonamide 1-77. N- (3,5-dihydroxyphenyl) -benzenesulfonamide 1-78. N- (3,5-dihydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-79. N- (3,5-dihydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-80. N-methyl-N- (3-hydroxyphenyl) -benzenesulfonamide 1-81. N-methyl-N- (3-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-82. N-methyl-N- (3-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-83. N-ethyl-N- (3-hydroxyphenyl) -benzenesulfonamide 1-84. N-ethyl-N- (3-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-85. Nn-propyl-N- (3-hydroxyphenyl)-(4'-ethylbenzene) sulfonamide 1-86. Nn-butyl-N- (3-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-87. Nn-butyl-N- (3-hydroxyphenyl)-(4'-phenylbenzene) sulfonamide 1-88. N- (2-hydroxyphenyl) -benzenesulfonamide 1-89. N- (2-hydroxyphenyl)-(4'-methylbenzene) sulfonamide 1-90. N- (2-hydroxyphenyl)-(4'-chlorobenzene) sulfonamide 1-91. N- (2-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-92. N- (4-methyl-2-hydroxyphenyl) -benzenesulfonamide 1-93. N- (5-Methoxy-2-hydroxyphenyl)-(4'-methoxybenzene) sulfonamide 1-94. N-methyl-N- (2-hydroxyphenyl)-(4'-methylbenzene) sulfonamide

In the compound represented by the general formula (2),
It is a sulfonic ester derivative having an amino group, and the substitution position of the sulfonic ester is 4-, 3- or 2-position with respect to the amino group, and more preferably,
This is the fourth or third position. That is, the general formula (2)
Compounds represented by -a) or general formula (2-b) are more preferred.

Embedded image [Wherein X ₂ , Z ₂ and R ₁₁ -R ₁₅ represent the same meaning as in the general formula (2)]

Specific examples of the compound represented by the general formula (2) include, for example, the following compounds, but of course, the present invention is not limited thereto.

-Exemplified Compound No. 2-1. (4-aminophenyl) -benzenesulfonic acid ester 2-2. (4-aminophenyl)-(2'-methylbenzene) sulfonic acid ester 2-3. (4-aminophenyl)-(3'-methylbenzene) sulfonic acid ester 2-4. (4-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-5. (4-aminophenyl)-(4'-ethylbenzene) sulfonic acid ester 2-6. (4-aminophenyl)-(4'-n-propylbenzene) sulfonic acid ester 2-7. (4-aminophenyl)-(4'-isopropylbenzene) sulfonic acid ester 2-8. (4-aminophenyl)-(4'-n-butylbenzene) sulfonic acid ester 2-9. (4-aminophenyl)-(4'-tert-butylbenzene) sulfonic acid ester 2-10. (4-aminophenyl)-(4'-n-pentylbenzene) sulfonate 2-11. (4-aminophenyl)-(4'-n-hexylbenzene) sulfonate 2-12. (4-aminophenyl)-(4'-cyclohexylbenzene) sulfonate 2-13. (4-aminophenyl)-(3 ', 4'-dimethylbenzene) sulfonate 2-14. (4-aminophenyl)-(3'-methoxybenzene) sulfonic acid ester 2-15. (4-aminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-16. (4-aminophenyl)-(4'-ethoxybenzene) sulfonic acid ester 2-17. (4-aminophenyl)-(4'-isopropoxybenzene) sulfonate 2-18. (4-aminophenyl)-(4'-n-butoxybenzene) sulfonate 2-19. (4-aminophenyl)-(4'-n-pentyloxybenzene) sulfonic acid ester 2-20. (4-Aminophenyl)-(4'-n-hexyloxybenzene) sulfonic acid ester 2-21. (4-Aminophenyl)-(3'-fluorobenzene) sulfonic acid ester 2-22. (4-aminophenyl)-(4'-fluorobenzene) sulfonic acid ester 2-23. (4-aminophenyl)-(2'-chlorobenzene) sulfonic acid ester 2-24. (4-aminophenyl)-(3'-chlorobenzene) sulfonic acid ester 2-25. (4-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-26. (2-Methyl-4-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-27. (3-Methyl-4-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-28. (3-methoxy-4-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-29. (2-Chloro-4-aminophenyl) -benzenesulfonic acid ester 2-30. (2-hydroxy-4-aminophenyl) -benzenesulfonic acid ester 2-31. (3-hydroxy-4-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-32. (4-N-methylaminophenyl) -benzenesulfonic acid ester 2-33. (4-N-methylaminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-34. (4-N-methylaminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-35. (4-N-ethylaminophenyl) -benzenesulfonic acid ester 2-36. (4-N-ethylaminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-37. (4-N-isopropylmethylphenyl)-(4'-methylbenzene) sulfonic acid ester 2-38. (4-N-n-butylaminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-39. (3-aminophenyl) -benzenesulfonic acid ester 2-40. (3-Aminophenyl)-(2'-methylbenzene) sulfonic acid ester 2-41. (3-Aminophenyl)-(3'-methylbenzene) sulfonic acid ester 2-42. (3-Aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-43. (3-Aminophenyl)-(4'-ethylbenzene) sulfonic acid ester 2-44. (3-Aminophenyl)-(4'-n-propylbenzene) sulfonate 2-45. (3-Aminophenyl)-(4'-isopropylbenzene) sulfonate 2-46. (3-Aminophenyl)-(4'-n-butylbenzene) sulfonic acid ester 2-47. (3-Aminophenyl)-(4'-tert-butylbenzene) sulfonate 2-48. (3-Aminophenyl)-(4'-n-pentylbenzene) sulfonate 2-49. (3-Aminophenyl)-(4'-n-hexylbenzene) sulfonate 2-50. (3-Aminophenyl)-(4'-cyclohexylbenzene) sulfonate 2-51. (3-Aminophenyl)-(3 ', 4'-dimethylbenzene) sulfonate 2-52. (3-Aminophenyl)-(3'-methoxybenzene) sulfonic acid ester 2-53. (3-Aminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-54. (3-Aminophenyl)-(4'-ethoxybenzene) sulfonic acid ester 2-55. (3-Aminophenyl)-(4'-isopropoxybenzene) sulfonate 2-56. (3-Aminophenyl)-(4'-n-butoxybenzene) sulfonic acid ester 2-57. (3-Aminophenyl)-(4'-n-pentyloxybenzene) sulfonic acid ester 2-58. (3-Aminophenyl)-(4'-n-hexyloxybenzene) sulfonic acid ester 2-59. (3-aminophenyl)-(3'-fluorobenzene) sulfonic acid ester 2-60. (3-Aminophenyl)-(4'-fluorobenzene) sulfonic acid ester 2-61. (3-Aminophenyl)-(2'-chlorobenzene) sulfonic acid ester 2-62. (3-Aminophenyl)-(3'-chlorobenzene) sulfonic acid ester 2-63. (3-Aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-64. (2-Methyl-3-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-65. (4-methyl-3-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-66. (5-methyl-3-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-67. (4-methoxy-3-aminophenyl) -benzenesulfonic acid ester 2-68. (5-chloro-3-aminophenyl) -benzenesulfonic acid ester 2-69. (5-hydroxy-3-aminophenyl) -benzenesulfonic acid ester 2-70. (5-hydroxy-3-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-71. (5-hydroxy-3-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-72. (3-N-methylaminophenyl) -benzenesulfonic acid ester 2-73. (3-N-methylaminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-74. (3-N-methylaminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-75. (3-N-ethylaminophenyl) -benzenesulfonic acid ester 2-76. (3-N-ethylaminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-77. (3-N-isopropylaminophenyl)-(4'-ethylbenzene) sulfonic acid ester 2-78. (3-N-n-butylaminophenyl) -nyl)-(4'-methylbenzene) sulfonic acid ester 2-79. (2-aminophenyl) -benzenesulfonic acid ester 2-80. (2-aminophenyl)-(4'-methylbenzene) sulfonic acid ester 2-81. (2-aminophenyl)-(4'-chlorobenzene) sulfonic acid ester 2-82. (2-aminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-83. (4-methyl-2-aminophenyl) -benzenesulfonic acid ester 2-84. (5-methoxy-2-aminophenyl)-(4'-methoxybenzene) sulfonic acid ester 2-85. (2-N-methylaminophenyl)-(4'-methylbenzene) sulfonic acid ester

In the compound represented by the general formula (3),
A sulfonamide derivative having a sulfonic acid ester group, and the substitution position of the sulfonic acid ester group is 4-, 3-, or 2-position with respect to the sulfonamide group;
More preferably, it is the 4-position or the 3-position. That is,
The compound represented by the general formula (3-a) or the general formula (3-b) is more preferable.

Embedded image [Wherein X ₃ , Z ₃ , R ₂₁ -R ₂₅ and R ₃₁ -R ₃₅ represent the same meaning as in formula (3)]

-Exemplified Compound No. 3-1. N- [4- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-2. N- [4- (2'-methylbenzenesulfonyloxy) phenyl]-(2 "-methylbenzene) sulfonamide 3- 3.N- [4- (3'-methylbenzenesulfonyloxy) phenyl]-(3" -Methylbenzene) sulfonamide 3-4. N- [4- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamido 3-5. N- [4- (4'-ethylbenzenesulfonyloxy) phenyl]-(4"- Ethylbenzene) sulfonamide 3-6. N- [4- (4'-n-propylbenzenesulfonyloxy) phenyl]-(4 "-n-propylbenzene) sulfonamide 3-7. N- [4- (4'-isopropylbenzenesulfonyloxy) phenyl Nyl]-(4 "-isopropylbenzene) sulfonamide 3-8. N- [4- (4'-n-butylbenzenesulfonyloxy) phenyl]-(4 "-n-butylbenzene) sulfonamide 3-9. N- [4- (4'-tert-butylbenzenesulfonyloxy) ) Phenyl]-(4 "-tert-butylbenzene) sulfonamide 3-10. N- [4- (4'-n-pentylbenzenesulfonyloxy) phenyl]-(4 "-n-pentylbenzene) sulfonamide 3-11. N- [4- (4'-n-hexylbenzenesulfonyloxy) ) Phenyl]-(4 "-n-hexylbenzene) sulfonamide 3-12. N- [4- (4'-cyclohexylbenzenesulfonyloxy) phenyl]-(4 "-cyclohexylbenzene) sulfonamide 3-13. N- [4- (3 ', 4'-dimethylbenzenesulfonyloxy) phenyl ]-(3 ", 4" -dimethylbenzene) sulfonamide 3-14. N- [4- (3'-methoxybenzenesulfonyloxy) phenyl]-(3 "-methoxybenzene) sulfonamide 3-15. N- [4- (4'-methoxybenzenesulfonyloxy) phenyl]-(4 "-methoxybenzene) sulfonamide 3-16. N- [4- (4'-ethoxybenzenesulfonyloxy) phenyl]-(4" -Ethoxybenzene) sulfonamide 3-17. N- [4- (4'-isopropoxybenzenesulfonyloxy) phenyl]-(4 "-isopropoxybenzene) sulfonamide 3-18.N- [4- (4'-n-butoxybenzenesulfonyloxy) phene Nyl]-(4 "-n-butoxybenzene) sulfonamide 3-19. N- [4- (4'-n-pentyloxybenzenesulfonyloxy) phenyl]-(4 "-n-pentyloxybenzene) sulfonamide 3-20.N- [4- (4'-n-hexyloxybenzene) Sulfonyloxy) phenyl]-(4 "-n-hexyloxybenzene) sulfonamide 3-21. N- [4- (3'-fluorobenzenesulfonyloxy) phenyl]-(3 "-fluorobenzene) sulfonamide 3-22. N- [4- (4'-fluorobenzenesulfonyloxy) phenyl]-(4" -Fluorobenzene) sulfonamide 3-23. N- [4- (2'-chlorobenzenesulfonyloxy) phenyl]-(2 "-chlorobenzene) sulfonamide 3-24. N- [4- (3'-chlorobenzenesulfonyloxy) phenyl]-(3" -chlorobenzene) Sulfonamide 3-25. N- [4- (4'-chlorobenzenesulfonyloxy) phenyl]-(4 "-chlorobenzene) sulfonamide 3-26. N- [4- (1'-naphthalenesulfonyloxy) phenyl]-(1" -naphthalene) Sulfonamide 3-27. N- [4- (2'-naphthalenesulfonyloxy) phenyl]-(2 "-naphthalene) sulfonamide 3-28. N- [2-methyl-4- (4'-methylbenzenesulfonyloxy) phenyl]-( 4 "-methylbenzene) sulfonamide 3-29. N- [3-methyl-4- (4'-chlorobenzenesulfonyloxy) phenyl]-(4 "-chlorobenzene) sulfonamide 3-30. N- [2-chloro-4- (benzenesulfonyloxy) phenyl] -benzene Sulfonamide 3-31.N- [3-hydroxy-4- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-32.N- [3-hydroxy-4- (4'-methylbenzenesulfonyloxy) Phenyl]-(4 "-methylbenzene) sulfonamide 3-33. N-methyl-N- [4- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-34. N-methyl-N- [4- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-35.N-methyl-N- [4- (4'-chlorobenzenesulfonyloxy) ) Phenyl]-(4 "-chlorobenzene) sulfonamide 3-36. N-ethyl-N- [4- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-37. N-ethyl-N- [4- (4'-methoxybenzenesulfonyloxy) phenyl]-(4 "-methoxybenzene) sulfonamide 3-38. N-isopropyl-N- [4- (4'-methylbenzene) Sulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-39. Nn-butyl-N- [4- (4 "-methylbenzenesulfonyloxy) phenyl]-(4" -methylbenzene) sulfonamide 3-40. N-methyl-N- [4- (1'-naphthalenesulfonyloxy) phenyl]-(1 "-naphthalene) sulfonamide 3-41. N- [3- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3- 42. N- [3- (2'-methylbenzenesulfonyloxy) phenyl]-(2 "-methylbenzene) sulfonamide 3-43. N- [3- (3'-methylbenzenesulfonyloxy) phenyl]-(3 "-methylbenzene) sulfonamide 3-44. N- [3- (4'-methylbenzenesulfonyloxy) phenyl]-(4" -Methylbenzene) sulfonamide 3-45. N- [3- (4'-ethylbenzenesulfonyloxy) phenyl]-(4 "-ethylbenzene) sulfonamide 3-46. N- [3- (4'-n-propylbenzenesulfonyloxy) phenyl]-(4 "-N-propylbenzene) sulfonamide 3-47. N- [3- (4'-isopropylbenzenesulfonyloxy) phenyl]-(4 "-isopropylbenzene) sulfonamide 3-48. N- [3- (4'-n-butylbenzenesulfonyloxy) phenyl] -(4 "-n-butylbenzene) sulfonamide 3-49. N- [3- (4'-tert-butylbenzenesulfonyloxy) phenyl]-(4 "-tert-butylbenzene) sulfonamide 3-50.N- [3- (4'-n-pentylbenzenesulfonyloxy) ) Phenyl]-(4 "-n-pentylbenzene) sulfonamide 3-51. N- [3- (4'-n-hexylbenzenesulfonyloxy) phenyl]-(4 "-n-hexylbenzene) sulfonamide 3-52. N- [3- (4'-cyclohexylbenzenesulfonyloxy) phenyl Enyl]-(4 "-cyclohexylbenzene) sulfonamide 3-53. N- [3- (3 ', 4'-dimethylbenzenesulfonyloxy) phenyl]-(3 ", 4" -dimethylbenzene) sulfonamide 3-54. N- [3- (3'-methoxybenzenesulfonyloxy) phenyl]-(3 "-methoxybenzene) sulfonamide 3-55.N- [3- (4'-methoxybenzenesulfonyloxy) phenyl]-(4" -Methoxybenzene) sulfonamide 3-56. N- [3- (4'-ethoxybenzenesulfonyloxy) phenyl]-(4 "-ethoxybenzene) sulfonamide 3-57. N- [3- (4'-isopropoxybenzenesulfonyloxy) phenyl]-( 4 "-isopropoxybenzene) sulfonamide 3-58. N- [3- (4'-n-butoxybenzenesulfonyloxy) phenyl]-(4 "-n-butoxybenzene) sulfonamide 3-59.N- [3- (4'-n-pentyloxybenzenesulfonyl) Oxy) phenyl]-(4 "-n-pentyloxybenzene) sulfonamide 3-60. N- [3- (4'-n-hexyloxybenzenesulfonyloxy) phenyl]-(4 "-n-hexyloxybenzene) sulfonamide 3-61. N- [3- (3'-fluorobenzenesulfonyloxy) Phenyl]-(3 "-fluorobenzene) sulfonamide 3-62. N- [3- (4'-fluorobenzenesulfonyloxy) phenyl]-(4 "-fluorobenzene) sulfonamide 3-63. N- [3- (2'-chlorobenzenesulfonyloxy) phenyl]-(2"- Chlorobenzene) sulfonamide 3-64. N- [3- (3'-chlorobenzenesulfonyloxy) phenyl]-(3 "-chlorobenzene) sulfonamide 3-65.N- [3- (4'-chlorobenzenesulfonyloxy) phenyl]-(4" -chlorobenzene) Sulfonamide 3-66. N- [3- (1'-naphthalenesulfonyloxy) phenyl]-(1 "-naphthalene) sulfonamide 3-67. N- [3- (2'-naphthalenesulfonyloxy) phenyl]-(2" -naphthalene) Sulfonamide 3-68. N- [2-methyl-3- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-69. N- [4-methyl-3- (4'-chlorobenzenesulfonyloxy) ) Phenyl]-(4 "-chlorobenzene) sulfonamide 3-70. N- [2-Chloro-3- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-71. N- [4-hydroxy-3- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-72. N- [4-hydroxy-3- (4'-methylbenzenesulfonoxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-73. N-methyl-N- [3- (benzenesulfonyloxy) phenyl -Benzenesulfonamide 3-74.N-methyl-N- [3- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-75. N-methyl-N- [3- (4'-chlorobenzenesulfonyloxy) phenyl]-(4 "-chlorobenzene) sulfonamide 3-76.N-ethyl-N- [3- (benzenesulfonyloxy) phenyl] -benzene Sulfonamide 3-77.N-ethyl-N- [3- (4'-methoxybenzenesulfonyloxy) phenyl]-(4 "-methoxybenzene) sulfonamide 3-78. N-isopropyl-N- [3- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-79.Nn-butyl-N- [3- (4'-methyl Benzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-80. N-methyl-N- [3- (1'-naphthalenesulfonyloxy) phenyl]-(1 "-naphthalene) sulfonamide 3-81. N- [2- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3- 82. N- [2- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-83. N- [2- (4'-chlorobenzenesulfonyloxy) phenyl]-(4 "-chlorobenzene) sulfonamide 3-84. N- [2- (4'-methoxybenzenesulfonyloxy) phenyl]-(4" -methoxy Benzene) sulfonamide 3-85. N- [4-methyl-2- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-86. N- [5-methoxy-2- (4'-methoxybenzenesulfonyloxy) phenyl]-(4 "-methoxybenzene) sulfonamide 3-87. N-methyl-N- [2- (4'-methylbenzene Sulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide

The compound represented by the general formula (1) according to the present invention can be prepared by a method known per se [for example, JP-A-57-200].
No. 340, J. Phys. Org. Chem. , 19,170
8 (1954)]. That is, for example, it can be produced by reacting a compound represented by the general formula (a) with a compound represented by the general formula (b).

Embedded image [Wherein X ₁ , Z ₁ and R ₁ -R ₅ represent the same meaning as in the general formula (1), and Y ₁ represents a halogen atom]

The compound represented by the general formula (2) according to the present invention can be prepared by a method known per se [for example, JP-A-57-200].
No. 340, J. Phys. Chem. Soc. , 1981
(1930)]. That is, for example, it can be produced by allowing a compound represented by the general formula (c) and a compound represented by the general formula (d) to act in the presence of a base (for example, triethylamine).

Embedded image [Wherein X ₂ , Z ₂ and R ₁₁ -R ₁₅ represent the same meaning as in the general formula (2), and Y ₂ represents a halogen atom]

The compound represented by the general formula (3) according to the present invention can be prepared by a known method [for example, see JP-A-57-200].
No. 340, J. Phys. Org. Chem. , 19,170
8 (1954)]. That is, for example, a compound represented by the general formula (e), a compound represented by the general formula (f) and a compound represented by the general formula (g) are converted into a base (for example, pyridine)
Can be produced by acting in the presence of

Embedded image [Wherein X ₃ , Z ₃ , R ₂₁ -R ₂₅ and R ₃₁ -R ₃₅ represent the same meaning as in the general formula (3), and Y ₃ and Y ₄ represent a halogen atom]

The heat-sensitive recording material of the present invention comprises, as an electron-accepting compound, at least one compound represented by the general formula (1) and a compound represented by the general formulas (2) and (3). The developer composition comprises a developer composition containing at least one selected compound (hereinafter, abbreviated as developer composition A).

The content of at least one compound selected from the compounds represented by the general formulas (2) and (3) in the developer composition A is not particularly limited. If the amount is 0.01 part by weight or more based on 100 parts by weight of the compound represented by the general formula (1), a sufficient effect is obtained. Even if the compounds represented by the general formulas (2) and (3) are contained in an excessively large amount, the effect does not change much. , At least one selected from compounds represented by general formulas (2) and (3)
Containing 0.01 to 10 parts by weight of a compound of the general formula (1).
The amount of at least one compound selected from the compounds represented by the general formulas (2) and (3) is 0.1 to 8 parts by weight, particularly preferably 0.1 to 8 parts by weight, per 100 parts by weight.
It is 2 to 6 parts by weight.

In the developer composition A, the compounds represented by the general formulas (1), (2) and (3) may be used alone or in combination. May be.

The method for preparing the developer composition A is not particularly limited. For example, 1) the general formula (1)
And at least one compound selected from the compounds represented by the general formulas (2) and (3) with respect to the compound represented by the general formula (1) and the compound represented by the general formula (1) Can be prepared by mixing the compound represented by the general formula (1) and the compound represented by the general formula (2) or / and the general formula (3).

Further, 2) when producing the compound represented by the general formula (1), the compound represented by the general formula (2) or / and the general formula (3) is formed as a by-product depending on the reaction conditions. (See, for example, Japanese Patent Application Laid-Open No. 57-20034).
0 can be referred to), so that the compound represented by the general formula (1) and the compound represented by the general formula (2) or / and the general formula (3) have a desired ratio. , And further purified and prepared as necessary.

The developer composition A prepared by the method 2) is
The compound represented by the general formula (1) and the compound represented by the general formula (2) or / and the general formula (3) may be preferable in that the composition is more uniformly mixed. .

The method of mixing the compound represented by the general formula (1) with the compound represented by the general formula (2) and / or (3) is not particularly limited.
For example, a compound represented by the general formula (1), a compound represented by the general formula (2) or / and the general formula (3), and a heat-fusible compound as required are mixed in a solid state. Method, or a compound represented by the general formula (1) and a compound represented by the general formula (2) or / and the general formula (3) in the presence of water.
And a heat-fusible compound, if desired,
A method of mixing can be applied. When mixing in the presence of water, for example, the mixing can be performed in the presence of a binder and a surfactant.

The temperature of the mixing treatment is not particularly limited. The reaction may be carried out at a temperature equal to or higher than the melting point of the compound represented by the general formula (1), (2) or / and (3).

When mixing, a suitable stirring and mixing device [for example, a mortar, a propeller type stirrer, a turbine type stirrer, a paddle type stirrer, a homogenizer, a homomixer,
Stirring and mixing equipment that does not use media such as line mixers and line homomixers, or agitating tank type mills such as attritors and sentry mills, flow tube type mills such as sand mills, grain mills, pearl mills, matter mills, and dyno mills, conical ball mills, It is preferable to use a stirring and mixing device filled with media (eg, glass beads, ceramic balls, steel balls, etc.) such as an annular type continuous wet stirring mill such as an annular mill.

The developer composition A produced and prepared as described above sometimes forms a solvate such as a hydrate, and the solvate is also added to the developer composition A. It is included and can be used as an electron accepting compound for the heat-sensitive recording material of the present invention. Of course, the developer composition A obtained by removing a solvent such as water from the solvate can also be used for the heat-sensitive recording material of the present invention.

In the heat-sensitive recording material of the present invention, the amount of the developer composition A of the present invention used as the electron-accepting compound is not particularly limited. 50 to 700 parts by weight
It is desirable to use about part by weight, preferably about 100 to 500 parts by weight.

The electron-accepting compound (developing agent) is a compound which acts on the electron-donating color-forming compound at the time of heating to form the electron-donating color-forming compound.

The electron-donating color-forming compound to be used in the heat-sensitive recording material of the present invention is not particularly limited. Thiazine compounds, fluoran compounds,
Various known electron-donating color-forming compounds such as pyridine-based compounds, spiro-based compounds, and fluorene-based compounds,
More preferred are fluoran compounds, and among them, fluoran compounds represented by the general formula (A) are preferred.

Embedded image (Where A and B are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkoxyalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a tetrahydrofurfuryl group And further, A and B may form a heterocyclic ring together with the nitrogen atom to which they are bonded,
Z ₁₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 1 carbon atom
To 4 alkoxy groups or halogen atoms; Z ₁₂ and Z ₁₃ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or a trifluoromethyl group)

Specific examples of the electron-donating color-forming compound include triarylmethane-based compounds.
3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide [“crystal violet lactone”], 3,3-bis (4-dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) −
3- (4-diethylamino-2-methylphenyl) -6
-Dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1,2-dimethylindole-3-
Yl) phthalide, 3- (4-dimethylaminophenyl)
-3- (2-methylindol-3-yl) phthalide,
3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide,
3,3-bis (2-phenylindol-3-yl)-
6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1-methylpyrrol-3-yl)
-6-dimethylaminophthalide and the like.

Examples of the vinylphthalide compound include 3,3-bis [1,1-bis (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, , 3-bis [1,1-bis (4
-Pyrrolidinophenyl) ethylene-2-yl] -4,
5,6,7-tetrabromophthalide, 3,3-bis [1
-(4-Dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-
Tetrachlorophthalide, 3,3-bis [1- (4-pyrrolidinophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, -[1,1-di (1-ethyl-2-methylindol-3-yl) ethylene-2-yl] -3- (4-
Diethylaminophenyl) phthalide, 3- [1,1-di (1-ethyl-2-methylindol-3-yl) ethylene-2-yl] -3- (4-N-ethyl-N-phenylaminophenyl) phthalide and so on.

Examples of the diarylmethane compound include 4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine,
N-2,4,5-trichlorophenylleuco auramine and the like.

The rhodamine-lactam compounds include:
For example, rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, rhodamine-B
-(4-chloroanilino) lactam and the like.

Examples of the thiazine compounds include, for example, 3,
7-bis (diethylamino) -10-benzoylphenoxazine, benzoylleucomethylene blue, 4-nitrobenzoylmethylene blue and the like.

As the fluoran compound, for example,
3,6-dimethoxyfluoran, 3-dimethylamino-
7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6,7-dimethylfluoran, 3-N-cyclohexyl-Nn-butylamino-7-methylfluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-
Octylaminofluoran, 3-diethylamino-7-
Di-n-hexylaminofluoran, 3-diethylamino-7-anilinofluoran, 3-diethylamino-7
-(2'-fluorophenylamino) fluoran, 3-
Diethylamino-7- (2'-chlorophenylamino)
Fluoran, 3-diethylamino-7- (3'-chlorophenylamino) fluoran, 3-diethylamino-7
-(2 ', 3'-dichlorophenylamino) fluoran, 3-diethylamino-7- (3'-trifluoromethylphenylamino) fluoran, 3-di-n-butylamino-7- (2'-fluorophenylamino) Fluoran, 3-di-n-butylamino-7- (2'-chlorophenylamino) fluoran, 3-N-isopentyl-
N-ethylamino-7- (2′-chlorophenylamino) fluoran, 3-Nn-hexyl-N-ethylamino-7- (2′-chlorophenylamino) fluoran, 3-diethylamino-6-chloro-7- Anilinofluoran, 3-di-n-butylamino-6-chloro-7
-Anilinofluoran, 3-diethylamino-6-methoxy-7-anilinofluoran, 3-di-n-butylamino-6-ethoxy-7-anilinofluoran, 3-pyrrolidino-6-methyl-7 -Anilinofluoran, 3-
Piperidino-6-methyl-7-anilinofluoran, 3
-Morpholino-6-methyl-7-anilinofluoran,
3-dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-
7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluoran, 3 -Nn-propyl-N-methylamino-6
-Methyl-7-anilinofluoran, 3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-n-butyl-N-methylamino-6
-Methyl-7-anilinofluoran, 3-N-n-butyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isobutyl-N-methylamino-6-
Methyl-7-anilinofluoran, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopentyl-N-ethylamino-6
Methyl-7-anilinofluoran, 3-N-n-hexyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-ethylamino-
6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-propylamino-6-methyl-7-
Anilinofluoran, 3-N-cyclohexyl-Nn
-Butylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-hexylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-octyl Amino-6-methyl-7
-Anilinofluoran, 3-N- (2'-methoxyethyl) -N-methylamino-6-methyl-7-anilinofluoran, 3-N- (2'-methoxyethyl) -N-ethylamino -6-methyl-7-anilinofluoran, 3
-N- (2'-methoxyethyl) -N-isobutylamino-6-methyl-7-anilinofluoran, 3-N-
(2'-ethoxyethyl) -N-methylamino-6-methyl-7-anilinofluoran, 3-N- (2'-ethoxyethyl) -N-ethylamino-6-methyl-7-anilinofur Oran, 3-N- (3'-methoxypropyl) -N-methylamino-6-methyl-7-anilinofluoran, 3-N- (3'-methoxypropyl) -N-
Ethylamino-6-methyl-7-anilinofluoran,
3-N- (3'-ethoxypropyl) -N-methylamino-6-methyl-7-anilinofluoran, 3-N-
(3′-ethoxypropyl) -N-ethylamino-6-
Methyl-7-anilinofluoran, 3-N-2′-tetrahydrofurfuryl-N-ethylamino-6-methyl-
7-anilinofluoran, 3-N- (4′-methylphenyl) -N-ethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-ethyl-7-anilinofluoran, 3-diethylamino-6-methyl-
7- (3′-methylphenylamino) fluoran, 3-
Diethylamino-6-methyl-7- (2 ′, 6′-dimethylphenylamino) fluoran, 3-di-n-butylamino-6-methyl-7- (2 ′, 6′-dimethylphenylamino) fluoran, 3 -Di-n-butylamino-
7- (2 ', 6'-dimethylphenylamino) fluoran, 2,2-bis [4'-(3-N-cyclohexyl-
N-methylamino-6-methylfluoran) -7-ylaminophenyl] propane, 3- [4 '-(4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluoran, 3- [4 '-(dimethylaminophenyl)] amino-5,7-dimethylfluoran and the like.

Examples of the pyridine compounds include 3-
(2-ethoxy-4-diethylaminophenyl) -3-
(1-octyl-2-methylindol-3-yl)-
4 or 7-azaphthalide, 3- (2-ethoxy-4-
Diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2- Methyl indole-
3- (yl) -4 or 7-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide, 3- ( 2-butoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide.

Examples of spiro compounds include 3-methyl-spiro-dinaphthopyran and 3-ethyl-spiro-pyran.
Dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3
-Propyl-spiro-dibenzopyran and the like.

As the fluorene compound, for example,
3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) phthalide, 3,6
-Bis (diethylamino) fluorene-9-spiro-
3 ′-(6′-dimethylamino) phthalide and the like.
Of course, the present invention is not limited to these electron-donating color-forming compounds, and these electron-donating color-forming compounds may be used alone or in combination.

The heat-sensitive recording material of the present invention is characterized by containing the developer composition A of the present invention as an electron-accepting compound, provided that the desired effects of the present invention are not impaired. It is also possible to use another electron accepting compound in combination. In this case, the ratio of the developer composition A to all the electron-accepting compounds is usually adjusted to 20% by weight or more, preferably 50% by weight or more, and more preferably 60% by weight or more. .

The electron-accepting compound other than the developer composition A of the present invention is not particularly limited. Various known electron accepting compounds such as an organic electron accepting compound and an inorganic electron accepting compound are exemplified.

Specific examples of the electron accepting compound other than the developer composition A of the present invention include, for example, 4-tert-butylphenol, 4-tert-octylphenol,
-Phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-
Octyl catechol, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 2,
2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 1,1-bis (4'-hydroxyphenyl) cyclohexane, 2,2-bis (4'-hydroxy-3'-methylphenyl) propane , 1,3-bis (4'-hydroxycumyl) benzene, 1,4-bis (4'-hydroxycumyl) benzene, 1,3,5-tris (4'-hydroxycumyl) benzene, bis ( 4-
(Hydroxyphenyl) acetic acid-n-butyl ester, 2,
2-bis (4'-hydroxyphenyl) acetic acid ethyl ester, 4,4- (4'-hydroxyphenyl) pentanoic acid-n-butyl ester, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid phenethyl ester, 2 4,4-dihydroxybenzoic acid phenoxyethyl ester, 4-hydroxyphthalic acid dimethyl ester,
Gallic acid-n-propyl ester, gallic acid-n-octyl ester, gallic acid-n-dodecyl ester, gallic acid-n-octadecyl ester, hydroquinone monobenzyl ether, bis (3-methyl-4-hydroxyphenyl) sulfide, Bis (2-methyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-
Hydroxyphenyl) sulfide, bis (3-cyclohexyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfone, bis (3-allyl-4)
-Hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4′-methyldiphenyl sulfone, 4-hydroxy-
4'-tert-butyldiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, 4-hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 4-
Hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-butoxydiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, 3,4- Dihydroxy-4'-methyldiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 2-methoxy-4'-hydroxydiphenylsulfone, 2-ethoxy-2'-hydroxydiphenylsulfone, 4-hydroxy-3-methyl-4 ' -N-propoxydiphenyl sulfone, bis (2-hydroxy-5
-Tert-butylphenyl) sulfone, bis (2-hydroxy-5-chlorophenyl) sulfone, bis [4-
(3′-hydroxyphenyloxy) phenyl] sulfone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 1,
7-di (4'-hydroxyphenylthio) -3,5-dioxaheptane, 1,5-di (4'-hydroxyphenylthio) -3-oxapentane, 2,4-dihydroxy-2'-methoxybenz Phenol derivatives such as anilide, or metal salts of these phenol derivatives (for example, metal salts such as nickel, zinc, aluminum and calcium), for example, 5- [4 ′-(2- [4-methoxyphenoxy] ethoxy) cumyl Salicylic acid, 4-
[3 ′-(4-methylphenylsulfone) propoxy]
Salicylic acid, 4- [2 '-(4-methoxyphenoxy)
Ethoxy] salicylic acid, 4-n-butyloxycarbonylaminosalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-nonyloxycarbonylaminosalicylic acid, 4-n-decyloxycarbonylaminosalicylic acid, 5-cyclohexyloxycarbonylamino Salicylic acid, 1-naphthoic acid, 2-naphthoic acid,
1-hydroxy-2-naphthoic acid, 2-hydroxy-3
-Naphthoic acid, 2-hydroxy-6-naphthoic acid, 1-
Acetyloxy-2-naphthoic acid, 2-acetyloxy-1-naphthoic acid, 2-acetyloxy-3-naphthoic acid, monobenzyl phthalate, monophenyl phthalate, isophthalic acid, terephthalic acid, 4-methylbenzoic acid Acid, 4-tert-butylbenzoic acid, 2-benzoylbenzoic acid, 2- (4'-chlorobenzoyl) benzoic acid, 4-nitrobenzoic acid, 4-chlorobenzoic acid, 4-
Trifluoromethylbenzoic acid, 4-formylbenzoic acid,
Organic acid derivatives such as 4-cyanobenzoic acid and stearic acid, or metal salts of these organic acid derivatives (for example,
Metal salts such as nickel, zinc, aluminum, and calcium), for example, complexes such as zinc thiocyanate antipyrine complex and acetylacetone molybdate complex, for example,
N, N'-diphenylthiourea, N, N'-di (3-trifluoromethylphenyl) thiourea, N, N'-di (3-chlorophenyl) thiourea, 1,4-di (3'-
Chlorophenyl) -3-thiosemicarbazide, N-phenyl-N ′-(4-methylphenylsulfone) urea,
Organic electron accepting compounds such as urea derivatives such as 4,4′-bis (4 ″ -methylphenylsulfonaminocarbonylamino) diphenylmethane, for example, acid clay, attapulgite, activated clay, aluminum chloride, zinc chloride,
Examples thereof include inorganic electron-accepting compounds such as zinc bromide, but are not limited to these compounds. These electron accepting compounds may be used in combination of two or more.

Further, the addition of a heat-fusible compound (compound having a melting point of about 70 to 150 ° C., more preferably a compound having a melting point of about 80 to 130 ° C.) as a sensitizer to the heat-sensitive recording layer is effective for high-speed recording. This is preferable for obtaining a corresponding heat-sensitive recording material. In this case, the amount of the heat-fusible compound used is not particularly limited, but is generally 10 to 700 parts by weight, preferably 20 to 500 parts by weight, per 100 parts by weight of the electron-donating chromogenic compound. It is desirable to do.

Specific examples of the heat-fusible compound include, for example, caproic amide, capric amide, palmitic amide, stearic amide, oleic amide, erucic amide, linoleic amide, linolenic amide, N- Ethyl capric amide, N-butyl lauric amide, N-methyl stearamide, N-methyl oleic amide, N-stearyl cyclohexyl amide, N-octadecyl acetamide, N-oleyl acetamide, stearyl urea, stearic anilide, linole Acid anilide, N-ethylcarbazole, 4-methoxydiphenylamine, N-hydroxymethylstearic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, acetanilide, 2-benzoylacetanilide Acetoacetanilide, 2'-methylacetoacetate anilide, 4'-methylacetoacetate anilide, 2 ', 4'-dimethyl acetoacetanilide, 2'
-Methoxyacetoacetic anilide, 4'-methoxyacetoacetic anilide, 2'-chloroacetoacetic anilide, 4 '
-Chloroacetoacetic anilide, 4'-chloro-2 ',
Nitrogen-containing compounds such as 5'-dimethoxyacetoacetic anilide, for example, benzyl 4-benzyloxybenzoate, phenyl 2-naphthoate, phenyl 1-hydroxy-2-naphthoate, dibenzyl oxalate, oxalic acid Di (4-methylbenzyl) ester, di (4-chlorobenzyl) oxalate, diphenyl adipate, diphenacyl glutarate, di (4-methylphenyl) carbonate, dimethyl terephthalate, dibenzyl terephthalate Ester compounds such as esters and methyl 4-benzoyloxybenzoate, for example, 4-benzylbiphenyl, m-terphenyl, 1,2-bis (3 ′, 4′-
Hydrocarbon compounds such as dimethylphenyl) ethane, fluorene, fluoranthene, 2,6-diisopropylnaphthalene and 3-benzylacenaphthene, for example, 2-benzyloxynaphthalene, 2- (4′-methylbenzyloxy) naphthalene, 1,4 -Diethoxynaphthalene,
1,2-diphenoxyethane, 1,2-bis (3′-methylphenoxy) ethane, 1-phenoxy-2- (4 ′
-Methylphenoxy) ethane, 1-phenoxy-2-
(4′-ethylphenoxy) ethane, 1- (4′-methoxyphenoxy) -2-phenoxyethane, 1- (4 ′
-Methoxyphenoxy) -2- (3'-methylphenoxy) ethane, 1- (4'-methoxyphenoxy) -2-
(2′-methylphenoxy) ethane, 1,2-bis (4′-methoxyphenylthio) ethane, 1,5-bis (4′-methoxyphenoxy) -3-oxapentane,
1,4-bis (2′-vinyloxyethoxy) benzene, 4- (4′-methylphenoxy) biphenyl,
4-dibenzyloxybenzene, 1,4-bis (2′-
Chlorobenzyloxy) benzene, 4,4'-di-n-
Butoxydiphenylsulfone, 4,4′-diallyloxydiphenylsulfone, 1,2-bis (phenoxymethyl) benzene, 1,2-diphenoxybenzene, 1,
4-bis (2'-chlorophenoxy) benzene, 1,4
-Bis (4'-methylphenoxy) benzene, 1,4-
Bis (3'-methylphenoxymethyl) benzene, 4-
Chlorobenzyloxy- (4'-ethoxybenzene),
4,4′-bis (phenoxy) diphenyl ether,
Ether compounds such as 4,4'-bis (phenoxy) diphenylthioether, 1,4-bis (4'-benzylphenoxy) benzene, and 1,4-bis [(4'-methylphenyloxy) methoxymethyl] benzene; , 1,4-diglycidyloxybenzene, 4-benzyloxy-4 '-(2-methylglycidyloxy) diphenylsulfone, 4- (4-methylbenzyloxy)-
Examples include epoxy compounds such as 4'-glycidyloxydiphenyl sulfone and N-glycidyl phthalimide, but are not limited thereto. These heat-fusible compounds may be used alone or in combination.

The heat-sensitive recording material of the present invention can be manufactured by a known method without using a special method. Generally, in the presence of water, an electron-donating color-forming compound, a developer composition A, and, if desired, a heat-fusible compound, a pigment, and the like, together or separately, are mixed with a ball mill, a sand mill ( (Vertical type, horizontal type), attritor, colloidal mill, etc., mixed and pulverized, usually pulverized and dispersed to a particle size of 3 μm or less, preferably 2 μm or less,
By mixing, a coating solution for the heat-sensitive recording layer can be prepared.

In the coating liquid for the heat-sensitive recording layer, a binder and a pigment are usually blended. The amount of the binder used is not particularly limited, but is generally about 5 to 50% by weight of the total solids.

As the binder, a water-soluble binder or a water-insoluble binder is generally used, and more preferably, a water-soluble binder is used.

Examples of the water-soluble binder include polyvinyl alcohol derivatives such as polyvinyl alcohol, carboxy-modified polyvinyl alcohol, sulfonated modified polyvinyl alcohol, and alkyl-modified polyvinyl alcohol, and cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. , Epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch, starch derivatives (oxidation Starch, etherified starch, etc.), casein, gelatin, gum arabic and the like.

As the water-insoluble binder, a synthetic rubber latex or a synthetic resin emulsion is generally used.
Examples thereof include styrene-butadiene rubber latex, acrylonitrile-butadiene latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. These binders may be used alone or in combination of two or more. Of course, a water-soluble binder and a water-insoluble binder can be used in combination.

The amount of the pigment to be used is not particularly limited, but generally, the electron-donating color-forming compound 100 is used.
About 50 to 700 parts by weight, preferably about 50 parts by weight,
It is desirable to use about 100 to 500 parts by weight.

As the pigment, for example, calcium carbonate,
Amorphous silica, amorphous calcium silicate, barium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, aluminum oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, wax, kaolin, clay, Diatomaceous earth, inorganic pigments such as silica, styrene microballs, nylon particles, urea-formalin fillers, polyethylene particles, cellulose fillers, starch particles, organic pigments such as silicone resin particles, but are not limited thereto. Not something.

These pigments may be used alone,
Alternatively, a plurality of them may be used in combination. Considering various characteristics of the thermal recording material (for example, compatibility with the thermal head),
The pigment is preferably a pigment having an oil absorption of 50 ml / 100 g or more according to the JIS K-5101 method, more preferably an inorganic pigment having an oil absorption of 50 ml / 100 g or more, and further preferably an oil absorption of 50 ml / 100 g. / 1
More than 00 g of calcium carbonate, amorphous silica, or amorphous calcium silicate.

Further, if necessary, a metal soap, a wax, a surfactant, an ultraviolet absorber, an ultraviolet stabilizer, a crosslinking agent, a hindered phenol compound, a phosphorus compound, An antifoaming agent or the like can be added. For example, by incorporating an ultraviolet absorber (ultraviolet stabilizer) and a hindered phenol compound into the heat-sensitive recording layer, the properties of the heat-sensitive recording material (eg, storage stability of a color image) can be further improved. There is.

Examples of the metal soap include metal salts of higher fatty acids such as zinc stearate, calcium stearate, aluminum stearate and zinc oleate.

Examples of the wax include paraffin wax, microcrystalline wax, carboxy-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, canderia wax, montan wax, and higher fatty acid esters.

As the surfactant (dispersant), for example,
Sulfosuccinic acid-based alkali metal salts [eg, di (n-
Hexyl) sulfosuccinic acid, di (2-ethylhexyl)
Sodium salts such as sulfosuccinic acid], sodium salts of dodecylbenzenesulfonic acid, sodium salts of lauryl alcohol sulfate, fatty acid metal salts, and fluorine-containing surfactants.

As the ultraviolet absorber (ultraviolet stabilizer),
Any compound that absorbs at least a part of ultraviolet light of about 300 to about 400 nm may be used. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, triazole derivatives, salicylic acid derivatives, cyanoacrylate derivatives, hindered amine derivatives, and the like. In particular, a triazole derivative is preferable as an ultraviolet absorber.

As the triazole derivative, for example, 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-ter
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5
Chlorobenzotriazole, 2- (2'-hydroxy-
3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Octylphenyl) benzotriazole and the like, but are not limited thereto. These triazole derivatives may be used alone,
Alternatively, a plurality of them may be used in combination.

The amount of the ultraviolet absorbent and the ultraviolet stabilizer is not particularly limited, but is generally 10 to 400 parts by weight based on 100 parts by weight of the electron-donating color-forming compound.
It is desirable to use about 10 parts by weight, preferably about 20 to 300 parts by weight.

Examples of the crosslinking agent include aldehyde derivatives such as glyoxal, epoxy compounds, polyamide resins, diglycidyl compounds, aziridine compounds, magnesium chloride, ferric chloride and the like.

As the hindered phenol compound, a phenol derivative in which at least one of the ortho positions of the phenolic hydroxyl group is substituted with a branched alkyl group is preferable. -Tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2,5-di-tert-octyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5 -Di-tert-octylhydroquinone,
1,1,3-tris (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) butane, 1,1,
3-tris (2′-methyl-4′-hydroxy-5′-
Cyclohexylphenyl) butane, 1,1,3-tris (2′-ethyl-4′-hydroxy-5′-tert-)
Butylphenyl) butane, 1,1,3-tris (3 ′,
5'-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (2'-methyl-4 '
-Hydroxy-5'-tert-butylphenyl) propane, 1,1-bis (2'-methyl-5'-tert-
Butyl-4'-hydroxyphenyl) butane, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis (3-tert-butyl-5-methyl) -2-hydroxyphenyl) methane, bis (3-tert-butyl-5-ethyl-2-hydroxyphenyl) methane,
1,3,5-trimethyl-2,4,6-tris (3 ′,
5'-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4'-tert-
Butyl-3'-hydroxy-2 ', 6'-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (4'-t
tert-butyl-3'-hydroxy-2'-methyl-
Examples thereof include, but are not limited to, 6'-ethylbenzyl) isocyanuric acid, bis (2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide. These hindered phenol compounds may be used alone or in combination.

The amount of the hindered phenol compound used is not particularly limited.
It is desirable to use about 10 parts by weight, preferably about 20 to 300 parts by weight.

As the phosphorus compound, a phosphite compound is preferable. For example, 2,2′-methylenebis (4 ″)
-Methyl-6 "-tert-butylphenyl) phosphate, 2,2'-methylenebis (4" -ethyl-6 "-
tert-butylphenyl) phosphate, 2,2′-
Methylenebis (4 ", 6" -di-tert-butylphenyl) phosphate, diphenylphosphate, bis (4-tert-butylphenyl) phosphate, bis (2,4-di-tert-butylphenyl) phosphate, bis (4 Examples thereof include -chlorophenyl) phosphate, bis (2-phenylphenyl) phosphate, bis (4-phenylphenyl) phosphate, and the like, and salts of these metals (for example, potassium, sodium, zinc, calcium, magnesium, and aluminum).

The heat-sensitive recording material of the present invention comprises a support having thereon a heat-sensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound, and further comprising a protective layer provided on the heat-sensitive recording layer. A thermosensitive recording material, which is a recording material, wherein a developer composition A is used as the electron-accepting compound.

That is, the form of the heat-sensitive recording material of the present invention is a heat-sensitive recording material in which a heat-sensitive recording layer is provided on a support, and a protective layer is further provided on the heat-sensitive recording layer. (2) a heat-sensitive recording material provided with an overcoat layer containing a water-soluble resin or a water-dispersible resin as a main component,
A heat-sensitive recording material further containing an ultraviolet absorber in the protective layer; (3) an intermediate layer mainly composed of a water-soluble resin or a water-dispersible resin as the protective layer; Thermosensitive recording material provided with an overcoat layer.

In the heat-sensitive recording material of the present invention, the method for forming the heat-sensitive recording layer is not particularly limited.
It can be formed according to a conventionally known technique. For example, a coating solution for a heat-sensitive recording layer is coated on a support with an appropriate coating device such as an air knife coater, a blade coater, a bar coater, a short dwell coater, a gravure coater, a curtain coater, a roll coater, and a wire bar. After drying, a heat-sensitive recording layer can be formed. When a plastic sheet is used as a support, the surface can be subjected to a treatment such as corona discharge or electron beam irradiation to increase the coating efficiency. still,
The coating amount of the heat-sensitive recording layer is not particularly limited, but is generally adjusted to about 1.5 to 12 g / m ² , preferably about ² to 10 g / m ² by dry weight.

Examples of the support include, but are not limited to, paper (for example, high-quality paper, art paper, coated paper, oil-resistant paper, recycled paper), and plastic (for example, polyethylene, polypropylene, polyester, polystyrene, (Nylon) sheet, synthetic paper, paper laminated with plastic, or a composite sheet or nonwoven sheet combining these, as well as a molded product and a metal deposited material. When the heat-sensitive recording material of the present invention is in the form of the above (3), the support may be a plastic sheet,
Synthetic paper is preferred.

The heat-sensitive recording material of the present invention also includes a form having a single layer or a plurality of undercoat layers (undercoat layers) between the support and the heat-sensitive recording layer.

By providing the undercoat layer, the color sensitivity can be further increased, and the dot reproducibility during printing can be increased.

In general, an undercoat layer (undercoat layer)
Are pigments or synthetic resins.

Examples of the pigment used in the undercoat layer include calcined kaolin, aluminum hydroxide, calcium carbonate, barium sulfate, zinc oxide, lithopone, laurite, kaolin, silica, and amorphous silica.
More preferably, it is calcined kaolin.

As the synthetic resin used for the undercoat layer, for example, styrene-acrylic resin, polystyrene resin, acrylic resin, polyethylene resin, polypropylene resin,
Polyacetal resins and the like can be mentioned, and more preferably, plastic spherical particles made of these synthetic resins, or plastic spherical hollow particles, preferably, plastic spherical particles having an average particle diameter of 0.5 to 3 μm, or It is a plastic spherical hollow particle, and more preferably, a plastic spherical particle or a plastic spherical hollow particle having a mean particle size of 0.5 to 3 μm composed of a styrene-acrylic resin.

The pigment and the synthetic resin may be used alone or in combination. Generally, a coating liquid for an undercoat layer is prepared as an aqueous dispersion by mixing a binder in addition to a pigment or a synthetic resin. Incidentally, as the binder, a binder used in forming the recording layer can be used. Further, if desired, a release agent, a water-proofing agent, a sizing agent (for example, alkenyl succinate, alkyl ketene dimer, rosin compound), a wax (for example, paraffin wax, Microcrystalline wax, carboxy-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, canderia wax, montan wax, higher fatty acid ester) and the like may be added.

The coating solution for the undercoat layer is applied to the support by a suitable coating device such as an air knife coater, blade coater, bar coater, short dwell coater, gravure coater, curtain coater, roll coater, wire bar, etc. It can be dried to form an undercoat layer. The amount of the undercoat layer is not particularly limited, but is generally 0.5 to 20 g by dry weight.
/ M ² , more preferably about 1 to 15 g / m ² . When the undercoat layer is mainly composed of a synthetic resin, the undercoat layer can be adjusted to an appropriate thickness (for example, 2 to 50 μm).

In the heat-sensitive recording material of the present invention, an intermediate layer or an overcoat layer is provided as a protective layer on the heat-sensitive recording layer thus obtained.

First, the first embodiment of the heat-sensitive recording material of the present invention, that is, (1) a heat-sensitive recording material having an overcoat layer containing a water-soluble resin or a water-dispersible resin as a main component as a protective layer is described. State.

The water-soluble resin or water-dispersible resin constituting the overcoat layer is not particularly limited, but in order to further enhance the effects of the present invention,
A resin having a tear strength of 1 kg / mm or more at 20 ° C. and 60% RH (relative humidity) of a formed film.
From the viewpoint of availability, more preferably, the tear strength is 1 kg / m.
m to 6 kg / mm, particularly preferably,
It is a resin having a tear strength of 1.5 kg / mm to 5 kg / mm. The tear strength refers to a resin having a surface temperature of 70 ° C., which is cast on a drum, dried, and dried to a thickness of 50 μm.
m at a temperature of 20 ° C. and 60 ° C.
% RH (relative humidity) is a value measured by an Elmendorf tear strength measuring instrument.

As the water-soluble resin or the water-dispersible resin,
For example, polyvinyl alcohol such as polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, sulfonated-modified polyvinyl alcohol, alkyl-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, and pyrrolidone-modified polyvinyl alcohol. Alcohol derivatives, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, casein, acacia, starch, starch derivatives (oxidized starch, etherified starch, etc.), styrene-butadiene copolymer, vinyl acetate-vinyl chloride-ethylene Copolymer, methacrylate-butadiene copolymer, etc. But are lower, the present invention is not limited to these. Preferably, it is a polyvinyl alcohol derivative, and particularly when a heat-sensitive recording material having a feel close to that of plain paper is produced, a polyvinyl alcohol derivative having a tear strength of 1 kg / mm to 6 kg / mm of a formed film. Is preferred.

The overcoat layer further contains a pigment. Examples of such pigments include the above-mentioned inorganic pigments and organic pigments, and these may be used alone or in combination. Particularly preferred pigments are calcium carbonate, silica, and starch particles, among which, when producing a heat-sensitive recording material having a feel similar to that of plain paper, the average particle size is 0.5 to 0.5.
2.0 μm calcium carbonate, average particle size 2.0-5.
0 μm silica is preferred. Although the amount of the pigment used is not particularly limited, it is usually 10 to 500 parts by weight, more preferably 40 parts by weight, per 100 parts by weight of the resin component.
４００400 parts by weight.

Next, a second embodiment of the heat-sensitive recording material of the present invention, that is, (2) a heat-sensitive recording material further containing an ultraviolet absorber in the protective layer will be described.

The protective layer in this case is obtained by further adding an ultraviolet absorber to the protective layer of the embodiment (1). still,
It is preferable that the ultraviolet absorber is encapsulated in the microcapsule.

The ultraviolet absorber is not particularly limited, and may be any compound that absorbs at least a part of ultraviolet light of about 300 to about 400 nm. Specific examples of the ultraviolet absorber include, for example, 2- (2′-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-
3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert)
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole,
-[2'-hydroxy-3 '-(3 ", 4", 5 ",
6 "-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-decyl-5 '
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-3′-undecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-
3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tetradecyl-5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-3′-pentadecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-hexadecyl-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy- 4'-
(2 "-ethylhexyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-4 '-(2" -ethylheptyloxy) phenyl] benzotriazole,
2- [2'-hydroxy-4 '-(2 "-ethyloctyloxy) phenyl] benzotriazole, 2- [2'
-Hydroxy-4 '-(2 "-propyloctyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-4'-(2" -propylheptyloxy) phenyl] benzotriazole, 2- [2'-hydroxy −
4 '-(2 "-propylhexyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-4'-
(1 "-ethylhexyloxy) phenyl] benzotriazole, 2,2-methylenebis [4 '-(1,1,
3,3-tetrabutyl) -6 ′-(2H-benzotriazol-2′-yl) phenol, polyethylene glycol (molecular weight about 300) and methyl-3- [3-tert
-Benzo-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, a benzotriazole-based ultraviolet absorber, phenyl salicylate, p-tert-butylphenyl salicylate, Salicylic acid-based UV absorbers such as p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone , 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-
Benzophenone ultraviolet absorbers such as sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, 2-ethylhexyl-2
A cyanoacrylate-based ultraviolet absorber such as -cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate;
6,6-tetramethyl-4-piperidyl) sebacate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, malonic acid (1,2,2,6,6-
Hindered amine-based ultraviolet absorbers such as pentamethyl-4-piperidyl) ester and the like, but are not limited thereto. These ultraviolet absorbers may be used alone or in combination of two or more. In particular,
Benzotriazole UV absorbers are preferred.

The ultraviolet absorber may be contained not in the overcoat layer but in the heat-sensitive recording layer. However, in order to further enhance the effect of the present invention, the ultraviolet absorber is contained in the overcoat layer. Is preferred.

The amount of the ultraviolet absorber used is not particularly limited, but is usually 0.05 to 2.0 g / m ² , more preferably 0.1 to 2.0 g / m ² , in the recording layer or the overcoat layer. It is adjusted to be about 1 to 1.0 g / m ² . The ultraviolet absorber may be included in a microcapsule, and the microcapsule can be prepared by various known methods. For example, it is prepared by a method of emulsifying and dispersing a core substance obtained by dissolving an ultraviolet absorber in an organic solvent in an aqueous medium, if necessary, and forming a wall film made of a polymer substance around an oily liquid. You.

[0093] The polymer substance serving as the wall film of the microcapsule is not particularly limited. For example, polyurethane / polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, Styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, gelatin, polyvinyl alcohol and the like can be mentioned. Particularly preferred are polyurethane / polyurea resins and aminoaldehyde resins.

A microcapsule having a polyurethane / polyurea resin wall film is a core for encapsulating a capsule wall film material such as a polyvalent isocyanate and a polyol which reacts with the polyisocyanate, or an adduct of a polyvalent isocyanate compound and a polyol compound. It is manufactured by mixing in a substance, emulsifying and dispersing in an aqueous medium in which a protective colloid substance such as polyvinyl alcohol is dissolved, heating, and performing a polymerization reaction at an oil droplet interface.

Examples of the polyvalent isocyanate compound used for producing microcapsules include m-phenylene diisocyanate, p-phenylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-
Diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexane-1,2-diisocyanate , Cyclohexane-
Diisocyanate compounds such as 1,4-diisocyanate; triisocyanate compounds such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and toluene-2,4,6-triisocyanate; 4,4′-dimethyldiphenylmethane-2, Tetraisocyanate compounds such as 2 ', 5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylenediisocyanate and trimethylolpropane, xylylene-1,4- Isocyanate prepolymers such as adducts of diisocyanate and trimethylolpropane, and the like.

The polyol compounds include, for example, ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 1,2-dihydroxybutane, 2,3-dihydroxybutane, 2,2-dimethyl-1,3-propanediol , 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4
-Cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, phenylethylene glycol, 1,
1,1-trimethylolpropane, hexanetriol, pentaerythritol, glycerin, 1,3-di (2′-hydroxyethoxy) benzene, 1,4-di (2′-hydroxyethoxy) benzene, m-xylylene glycol, p-xylylene glycol, α, α'-
Dihydroxy-p-diisopropylbenzene, 4,4 '
-Dihydroxydiphenylmethane, 2,2-bis (4 ′
-Hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and the like. A plurality of polyvalent isocyanate compounds and polyol compounds can be used in combination, if desired.

Microcapsules having a wall film made of an aminoaldehyde resin are manufactured by a method in which a wall material is added after emulsification of a core substance. There is also the advantage of being able to adjust. Microcapsules having a wall membrane made of an aminoaldehyde resin are usually at least one amine compound such as urea, thiourea, alkyl urea, ethylene urea, acetoguanamine, benzoguanamine, melamine, guanidine, biuret, cyanamide, and formaldehyde, At least one aldehyde compound such as acetaldehyde, paraformaldehyde, hexamethylenetetramine, glutaraldehyde, glyoxal, and furfural, or an initial reactive condensate obtained by condensing them;
-It is manufactured by the situ method.

As an emulsifier (protective colloid agent) used for microencapsulation, various anionic, nonionic, cationic or amphoteric water-soluble polymer compounds are used. The amount of the emulsifier used is not particularly limited. For example, when a polyurethane / polyurea resin is used as a wall film material, the amount is usually based on the total of the wall film material, the ultraviolet absorber, and the organic solvent. , 1 to 50% by weight, preferably 3 to 30% by weight. When an aminoaldehyde resin is used as a wall film material, the amount of the emulsifier used is usually 1 to 20% by weight,
Preferably, it is 3 to 10% by weight.

The organic solvent is not particularly limited, but examples thereof include those used in pressure-sensitive recording materials and the like.
Various high boiling organic solvents can be used. Specific examples of the organic solvent include, for example, tricresyl phosphate, trioctyl phosphate, dibutyl phthalate, dioctyl phthalate, butyl oleate, ester organic solvents such as diethylene glycol dibenzoate, isopropyl naphthalene,
Diisopropylnaphthalene, 1-methyl-1-phenyl-1-tolylmethane, 1-methyl-1-phenyl-1-
Examples thereof include aromatic organic solvents such as xylylmethane, 1-phenyl-1-tolylmethane, and isopropylbiphenyl, and further, cottonseed oil, castor oil, kerosene, paraffin, chlorinated paraffin, and naphthenic oil. These may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, but an amount sufficient to sufficiently dissolve the ultraviolet absorber in the microcapsules is used. For example, when a polyurethane / polyurea resin is used as the wall film material, the organic solvent is usually 10 to 60% by weight, preferably 20 to 20% by weight, based on the total of the organic solvent, the ultraviolet absorber and the microcapsule wall film material. 60% by weight. When an aminoaldehyde resin is used as a wall film material, the amount of the organic solvent used is usually 50 to 2 to the ultraviolet absorbent.
000% by weight, preferably 100 to 1000% by weight. In addition, when an ultraviolet absorbent that is liquid at normal temperature is used, an organic solvent need not be used.

The amount of the microcapsule wall material used is not particularly limited. For example, when a polyurethane / polyurea resin is used as the wall material, an organic solvent, an ultraviolet absorber, and a microcapsule wall film may be used. It is usually 37 to 75% by weight, preferably 35 to 60% by weight, based on the total of the materials, and when an aminoaldehyde resin is used as a wall film material, an ultraviolet absorber,
Usually, based on the total amount of the organic solvent used as needed,
30 to 300% by weight, preferably 35 to 200% by weight
It is.

Regarding the amount of the ultraviolet absorber used,
Although not particularly limited, for example, polyurethane
When a polyurea resin is used as the wall material, it is usually 3 to 50% by weight, preferably 3 to 2% by weight based on the total of the organic solvent, the ultraviolet absorber and the microcapsule wall material.
0% by weight, and when an aminoaldehyde resin is used as the wall film material, it is usually 3 to 75% based on the total of the ultraviolet absorber, the microcapsule wall film material, and the organic solvent used as required. %, Preferably 3 to 50% by weight. In addition, various additives such as an antioxidant and a release agent can be added to the microcapsules as needed in addition to the ultraviolet absorber. In microencapsulation, a reaction accelerator such as a tin compound, a polyamide compound, an epoxy compound, or a polyamine compound may be used in combination.

The average particle size of the microcapsules is not particularly limited, but is usually 0.1 to 5 μm, preferably 0.3 to 3 μm. The amount of the microcapsules in the heat-sensitive recording layer or the overcoat layer is not particularly limited, but is usually 5 to 80% by weight, preferably 15 to 70% by weight based on the total solid content of each layer. % By weight.

In the forms (1) and (2) of the heat-sensitive recording material of the present invention, the coating liquid for forming the overcoat layer is as follows:
An aqueous coating solution is prepared by mixing and dispersing with a mixing machine such as a ball mill, an attritor, a homogenizer and the like, and is coated on the heat-sensitive recording layer by various known coating apparatuses to form an overcoat layer. Further, in the coating liquid for forming the overcoat layer, various additives that may be added to the heat-sensitive recording layer, for example, metal soap, wax, surfactant, crosslinking agent, antifoaming agent and the like are added. Is also good. The amount of the coating liquid for forming the overcoat layer is not particularly limited, but is generally 0.1% by dry weight.
About 20 to 20 g / m ² , preferably 0.5 to 10 g / m ²
It is prepared in the range of about.

Next, the third embodiment of the heat-sensitive recording material of the present invention, that is, (3) an intermediate layer containing a water-soluble resin or a water-dispersible resin as a main component and an ionizing radiation-curable resin as a protective layer. A heat-sensitive recording material provided with an overcoat layer will be described. In this case, first, an intermediate layer is provided on the heat-sensitive recording layer, and then an overcoat layer containing an ionizing radiation-curable resin as a main component is provided on the intermediate layer. In forming the intermediate layer, a water-soluble resin or a water-dispersible resin used in forming the overcoat layer (1) or (2) is used, and a polyvinyl alcohol derivative is particularly preferable. In addition, the above-mentioned various inorganic pigments and organic pigments can be added to the intermediate layer, and the amount of the pigment used is usually 10 to 500 parts by weight, more preferably 80 to 500 parts by weight, based on 100 parts of the resin component. 350 parts by weight. Further, in the coating liquid for forming the intermediate layer, various additives that may be added to the heat-sensitive recording layer, for example, metal soap, wax, surfactant, ultraviolet absorber, ultraviolet stabilizer, crosslinking agent, A foaming agent may be added.

The coating liquid for forming the intermediate layer is usually prepared as an aqueous coating liquid, and if necessary, mixed and dispersed by means of a ball mill, an attritor or the like and a stirrer. It is applied on the heat-sensitive recording layer to form an intermediate layer. After the application, curing and drying can be performed by irradiating ultraviolet rays or electron beams.

The coating amount of the coating liquid for forming the intermediate layer is not particularly limited, but is generally about 0.1 to 20 g / m ² , preferably 0.5 to ²⁰ g / m ^{2 in} dry weight.
It is prepared in a range of about 10 g / m ² .

For the purpose of increasing the smoothness of the surface of the intermediate layer, it is preferable to carry out a smoothing treatment with a super calender or the like. In this case, the Bekk smoothness of the surface of the intermediate layer is 50 seconds or more, more preferably 300 seconds. It is adjusted to at least 2,000 seconds, particularly preferably at least 3,000 seconds.

An overcoat layer containing an ionizing radiation-curable resin is provided on the intermediate layer thus obtained. As the ionizing radiation curable resin forming the overcoat layer, for example, various prepolymers or monomers are used.

Examples of the prepolymer include:-aliphatic or aromatic-substituted aliphatic dihydric and hexavalent polyhydric alcohols and polyalkylene glycol poly (meth)
Acrylates, poly (meth) acrylates of polyhydric alcohols in which alkylene oxide is added to aliphatic or aromatic-substituted aliphatic polyhydric alcohols having 2 to 6 valences, poly (meth) acryloyloxyalkyl phosphate ester・ Polyester poly (meth) acrylate, ・ Epoxy poly (meth) acrylate, ・ Polyurethane poly (meth) acrylate, ・ Polyamide poly (meth) acrylate, ・ Polysiloxane poly (meth) acrylate, ・ On the side chain and / or terminal Vinyl- or diene-based low molecular weight polymers having a (meth) acrylate group; and prepolymers such as the above-mentioned oligoester (meth) acrylate modified products.

Examples of the monomer include a carboxyl group-containing monomer such as an ethylenically unsaturated mono- or polycarboxylic acid and a carboxylic acid group-containing monomer such as an alkali metal salt, an ammonium salt or an amine salt thereof; Amide group-containing monomers such as unsaturated (meth) acrylamide or alkyl-substituted (meth) acrylamide, N-vinylpyrrolidone; Sulfone group-containing monomers such as aliphatic or aromatic vinyl sulfone and alkali metal salts, ammonium salts, amines thereof Sulfonate group-containing monomers such as salts; Hydroxyl group-containing monomers such as ethylenically unsaturated ethers; Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate-2-vinylpyridine; Quaternary ammonium group-containing monomers An alkyl ester of an ethylenically unsaturated carboxylic acid; a monomer containing a nitrile group such as (meth) acrylonitrile; an ester of an ethylenically unsaturated alcohol such as vinyl acetate or (meth) allyl acetate; an alkylene of a compound having active hydrogen Mono (meth) acrylates of oxide addition polymers, diesters with polycarboxylic acids or unsaturated alcohols, or ester group-containing polyfunctional monomers such as polyesters, and alkylene oxide addition polymers of compounds having active hydrogen and mono ( (B) Multifunctional monomer composed of diester with meth) acrylic acid or polyester, bisacrylamide such as N, N-methylenebisacrylamide, styrene, divinylbenzene, divinylethylene glycol, divinylsulfene, divinyl Ether, divinyl ketone, such as a monofunctional or polyfunctional monomer such as trivinyl benzene. These prepolymers and monomers may be used alone or in combination.

Particularly preferred is an ionizing radiation curable resin having a glass transition point (Tg) of 150 ° C. or higher after curing. Specific examples thereof include pentaerythritol triacrylate, trimethylolpropane triacrylate, Examples include polyfunctional monomers such as pentaerythritol hexaacrylate and tris (acryloxyethyl) isocyanurate, polysiloxane polyacrylates, and tetrafunctional or higher oligoester acrylates.

Incidentally, if necessary, the above-mentioned various inorganic pigments and organic pigments can be contained in the ionizing radiation curable resin layer. Incidentally, the pigment usually has an average particle diameter of 15 μm.
m or less, preferably 5 μm or less.

The ionizing radiation-curable resin may further contain, if desired, a non-ionizing radiation-curable resin (for example, acrylic resin, alkyd resin, silicon resin, fluororesin, butyral resin, etc.), wax, surfactant, Various additives such as an ultraviolet absorber may be added.

The ionizing radiation-curable resin component may be a mixer or the like.
Any suitable mixing, mixing by a stirrer,
It is applied on the above by various known methods. About application amount
Is not particularly limited, but is usually 0.1 to 20.
g / m^TwoDegree, more preferably 0.3 to 10 g / m About
Prepared each time.

Examples of ionizing radiation for curing the ionizing radiation-curable resin include, for example, electron beams, ultraviolet rays, α rays,
Examples include β-rays, γ-rays, and X-rays, and in consideration of safety and the like, electron beams or ultraviolet rays are more preferable. The amount of ionizing radiation used is, for example, usually about 0.1 to 15 Mrad, more preferably about 0.5 to 10 Mrad when using an electron beam.

In the case of the electron beam radiation system, for example, a scanning system, a curtain beam system, a broad beam system, or the like is used as the radiation system.
Irradiation is performed at an acceleration voltage of about 300 KV.

In the case of the ultraviolet radiation system, the components of the ionizing radiation-curable resin include thioxanthone, benzoin, dimethylxanthone, benzophenone, anthracene, benzyldimethylketal, anthraquinone, 1-chloroanthraquinone, 2-ethylanthraquinone, and 2-tert-thraquinone.
A photosensitizer such as butylanthraquinone is added.

The addition amount of the photosensitizer is usually about 0.1 to 10% by weight, more preferably about 0.3 to 5% by weight, based on the ionizing radiation-curable resin.

For the purpose of accelerating the curing, in addition to the photosensitizer, for example, triethanolamine, 2-dimethylaminoethanol, dimethylaminobenzoic acid, dimethylaminobenzoic acid amyl ester, dimethylaminobenzoic acid lauryl ester Such tertiary amines can be added in an amount of about 0.05 to 5% by weight based on the ionizing radiation-curable resin.

In the case of the ultraviolet radiation system, it is usually 500 to 8
Irradiation with ultraviolet light having an intensity of about 000 μW / cm is performed. As the light source, for example, an ultraviolet lamp (for example, a low-pressure, medium-pressure or high-pressure mercury lamp), a xenon lamp, a tungsten lamp and the like can be used.

The heat-sensitive recording material of the present invention may further comprise, if necessary, a protective layer (backcoat layer) on the back surface of the heat-sensitive recording layer.
Or an intermediate layer made of a pigment, a binder, or the like may be provided between the heat-sensitive recording layer and the undercoat layer, or between the heat-sensitive recording layer and the backcoat layer. Further, various known techniques in a method for producing a heat-sensitive recording material, such as applying an adhesive treatment to the back surface of the support, processing the adhesive label, and producing a heat-sensitive recording label, can be provided. Further, it is preferable that, after the formation of the undercoat layer, the heat-sensitive recording layer, and / or the protective layer, for example, a super-calender treatment is performed to improve smoothness.

The heat-sensitive recording material of the present invention can be used, for example, for facsimile, printer, business card, postcard, prepaid card, etc., tag label, food label, bar code label, distribution label, etc., ATM. −
It can be used for various applications to which heat-sensitive recording materials are applied, such as for CDs, handy terminals, for thermosensitive magnetic recording, for tickets such as entrance tickets and tickets, and for video printers.

[0124]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the present invention is not limited thereto. In addition, unless otherwise indicated,% represents weight%.

Production Example 1 Preparation Example of Developer Composition 22 g of 4-aminophenol, 38 g of 4-methylbenzenesulfonyl chloride and 16 g of pyridine were stirred in 200 ml of dichloromethane at room temperature for 4 hours. After washing the reaction mixture with water, a dichloromethane solution was separated, and dichloromethane was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of dichloromethane and petroleum ether to give colorless crystals 4.
4 g were obtained. The crystals were analyzed by high performance liquid chromatography to find that N- (4-hydroxyphenyl)-
(4′-methylbenzene) sulfonamide (compound of Exemplified Compound No. 1-4) 97%, (4-aminophenyl)
-(4'-methylbenzene) sulfonic acid ester (compound of Exemplified Compound No. 2-4) 0.05%, N- [4-
(4'-methylbenzenesulfonyloxy) phenyl]
-(4 "-methylbenzene) sulfonamide (compound of Exemplified Compound No. 3-4) 2.95%, which was used as a developer composition as an electron acceptor for a thermosensitive recording material. It was used as an active compound.

Example 1 3-Di-n-butylamino-6-methyl-7-anilinofluorane was used as the electron-donating color-forming compound, and 2-benzyloxynaphthalene was used as the heat-fusible compound. Using a developer composition prepared by the method described in Production Example 1 as an electron accepting compound, a thermosensitive recording material was produced by the following method.

[Preparation of Thermosensitive Recording Material] (1) Formation of Thermosensitive Recording Layer (Composition A) Electron-donating color-forming compound 10 g Heat-fusible compound 20 g 5% methylcellulose aqueous solution 20 g Water 50 g ------ ――――――――――――――――――――――――― Total 100g (B composition) Electron acceptor compound 20g 5% methylcellulose aqueous solution 30g Water 50g ―――――― ―――――――――――――――――――――――――― Total 100g The above solution A and solution B were each sand-milled to an average particle size of 1.5 μm. And a dispersion was prepared. Next, 100 g of solution A, 100 g of solution B, 10 g of 30% paraffin wax, and calcium carbonate [Shiroishi Kogyo Callite KT] 10 with an oil absorption of 138 ml / 100 g
g, 20% oxidized starch aqueous solution 75 g, 20% polyvinyl alcohol (Kuraray PVA-105) aqueous solution 75 g
Were mixed and stirred to prepare a coating solution for the recording layer. The coating liquid was applied on a high-quality paper (basis weight: 50 g / m ² ) with a dry coating amount of 5.5 g.
/ M ^2, and then subjected to a super calender treatment after being dried.

(2) Formation of overcoat layer On the obtained heat-sensitive recording layer, a coating solution (C
Liquid) was applied so that the coated amount after drying was 2.0 g / m ² , dried, and then subjected to a super calender treatment to form an overcoat layer, thereby producing a thermosensitive recording material. still,
In liquid C, polyvinyl alcohol is made by Kuraray PV
A-117 (tear strength 4.0 kg / m ² at 20
° C, 60% RH). Calcium carbonate is Shiroishi Kogyo's light calcium carbonate PC with an average particle size of 1.5 μm.
Was used. The silica used was Nippon Silica Nip Seal E-150J (average particle diameter 4 μm). (C solution composition) 10% aqueous solution of polyvinyl alcohol 800 g Calcium carbonate 10 g Silica 10 g Water 100 g ―――――――――――――――――――――――――――――――― 920g in total

Examples 2 to 13 In Example 1, the combination of the electron-donating color-forming compound, the heat-fusible compound and the electron-accepting compound in Solution A shown in Table 1 (combination number 2) To 13), a heat-sensitive recording material was produced in accordance with the method described in Example 1, except that each was used. In Table 1, the heat-fusible compound a was 2-
Benzyloxynaphthalene, heat fusible compound b,
1,2-bis (3′-methylphenoxy) ethane, the heat-fusible compound c is 4- (4′-methylphenoxy) biphenyl, and the heat-fusible compound d is di (4-methyl oxalate). Benzyl) ester, heat-fusible compound e is diphenyl adipate, heat-fusible compound f is N
-Hydroxymethylstearic acid amide, the heat-fusible compound g is 2'-methylacetoacetic anilide, the heat-fusible compound h is 4-benzylbiphenyl, and the heat-fusible compound i is 1,4- Dibenzyloxybenzene, heat-fusible compound j, 4,4′-diallyloxydiphenylsulfone, heat-fusible compound k, terephthalic acid dimethyl ester, heat-fusible compound l, 1,2 -Bis (3 ', 4'-dimethylphenyl) ethane.
The electron accepting compounds A-1 to A-10 in Table 1 are:
The electron-accepting compounds (developing agent compositions) shown in Table 2 are shown. Incidentally,% in Table 2 represents% by weight in the composition.

[0130]

[Table 1]

[0131]

[Table 2]

Example 14 Instead of using 25 g of calcium carbonate [Shiraishi Kogyo Callite KT] having an oil absorption of 138 ml / 100 g in Example 1, amorphous silica having an oil absorption of 170 ml / 100 g [Mizusawa Co., Ltd.] A thermosensitive recording material was prepared according to the method described in Example 1, except that 40 g of P527 was used.

Example 15 Instead of using 25 g of calcium carbonate [Shiraishi Kogyo Callite KT] having an oil absorption of 138 ml / 100 g in Example 1, amorphous calcium silicate [oil having an oil absorption of 145 ml / 100 g] was used. Mizusawa Chemical's P832] 20
Except for using g, according to the method described in Example 1,
A heat-sensitive recording material was produced.

Example 16 In Example 1, a paper provided with an undercoat layer (undercoat layer) prepared by the following method was used instead of using high-quality paper (basis weight: 50 g / m ² ). According to the method described in Example 1, a heat-sensitive recording material was produced. [Production of paper provided with undercoat layer] Calcined kaolin (ansi
lex90, manufactured by Engelhardt) 80 g, 0.5%
A 160% aqueous solution of sodium hexametaphosphate was dispersed with a homogenizer, and a 10% aqueous solution of polyvinyl alcohol (Kuraray PVA-105) was added to the dispersion.
g was added and stirred sufficiently to prepare a coating solution for an undercoat layer. After applying and drying the coating solution on a high-quality paper (basis weight 50 g / m ² ) so that the dry coating amount is 7.0 g / m ² ,
The paper provided with the undercoat layer was produced by performing a super calender treatment.

Example 17 In Example 1, a paper provided with an undercoat layer (undercoat layer) prepared by the following method was used instead of using high-quality paper (basis weight: 50 g / m ² ). According to the method described in Example 1, a heat-sensitive recording material was produced. [Preparation of paper provided with undercoat layer] Average particle size is 1.0 μm
In 400 g of an aqueous dispersion of spherical hollow particles made of 25% styrene-acrylic resin having a porosity of 51% (volume ratio),
40 g of styrene-butadiene rubber latex and 10 g of water were added, and the mixture was sufficiently stirred to prepare a coating liquid for an undercoat layer. The coating liquid is applied on a high-quality paper (basis weight 50 g / m ² )
After coating and drying to a thickness of μm, the paper was subjected to a super calender treatment to prepare a paper provided with an undercoat layer.

Example 18 In Example 1, 10 g of wheat starch was further added to the solution C.
Was added, and a heat-sensitive recording material was produced in accordance with the method described in Example 1, except that an overcoat layer was formed.

Example 19 In Example 1, a 10% polyvinyl alcohol solution C [PVA-117 manufactured by Kuraray (tear strength: 4.0 kg / mm) was used.
at 20 ° C., 60% RH)]
0% polyvinyl alcohol [Kuraray's PVA-124
(Tear strength: 1.6 kg / mm at 20 ° C., 60% RH)] A heat-sensitive recording material was prepared according to the method described in Example 1, except that an aqueous solution was used.

Example 20 In Example 1, 10% polyvinyl alcohol of solution C [Kuraray PVA-117 (tear strength: 4.0 kg / mm) was used.
at 20 ° C., 60% RH)]
0% polyvinyl alcohol [Kuraray PVA-217]
(Tear strength: 5.0 kg / mm at 20 ° C., 60% RH)] A heat-sensitive recording material was prepared according to the method described in Example 1, except that an aqueous solution was used.

Example 21 In Example 1, 10% polyvinyl alcohol solution C [PVA-117 manufactured by Kuraray (tear strength: 4.0 kg / mm) was used.
at 20 ° C., 60% RH)]
0% alkyl-modified polyvinyl alcohol [Kuraray MP
-107 (tear strength 2.1 kg / mm at 20 ° C,
60% RH)] A heat-sensitive recording material was prepared according to the method described in Example 1 except that an aqueous solution was used.

Example 22 In Example 1, a 10% polyvinyl alcohol solution C [PVA-117 manufactured by Kuraray (tear strength: 4.0 kg / mm) was used.
at 20 ° C., 60% RH)]
0% polyvinyl alcohol [Kuraray PVA-105]
(Tear strength 0.8 kg / mm at 20 ° C, 60% R
H)] A heat-sensitive recording material was prepared according to the method described in Example 1 except that an aqueous solution was used.

Example 23 In Example 1, the electron accepting compound in Solution B was
Instead of using 20 g of the developer composition prepared in Production Example 1, 16 g of the developer composition prepared in Production Example 1, and 1,1,3-tris (2 ′) as a hindered phenol
-Methyl-4'-hydroxy-5'-tert-butylphenyl) butane was used in the same manner as in Example 1 except that 8 g of the thermosensitive recording material was used.

Example 24 In Example 1, the electron accepting compound in Solution B was
Instead of using 20 g of the developer composition prepared in Production Example 1, 16 g of the developer composition prepared in Production Example 1, and 2- (2′-hydroxy-5′-methylphenyl) as an ultraviolet absorber A heat-sensitive recording material was produced according to the method described in Example 1, except that 8 g of benzotriazole was used.

Example 25 In Example 1, the electron accepting compound in the solution B was
Instead of using 20 g of the developer composition prepared in Production Example 1, 16 g of the developer composition prepared in Production Example 1 and 4 g of 1,4-bis (4′-hydroxycumyl) benzene
A heat-sensitive recording material was prepared according to the method described in Example 1 except that was used.

Example 26 In Example 1, the electron accepting compound in Solution B was
Example 1 was repeated except that, in place of using 20 g of the developer composition prepared in Production Example 1, 12 g of the developer composition prepared in Production Example 1 and 8 g of 2,4′-dihydroxydiphenylsulfone were used. A heat-sensitive recording material was prepared according to the method described in (1).

Example 27 In Example 1, the electron accepting compound in Solution B was
Instead of using 20 g of the developer composition prepared in Production Example 1, except that 17 g of the developer composition prepared in Production Example 1 and 3 g of 4-hydroxy-4′-isopropoxydiphenylsulfone were used. According to the method described in Example 1, a heat-sensitive recording material was produced.

Comparative Example 1 In Example 1, the electron accepting compound in Solution B was
Instead of using the developer composition prepared in Production Example 1,
A heat-sensitive recording material was prepared according to the method described in Example 1, except that N- (4-hydroxyphenyl) -benzenesulfonylamide was used.

Comparative Example 2 In Example 1, the electron accepting compound in Solution B was
Instead of using the developer composition prepared in Production Example 1,
Example 1 except that N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonylamide was used.
A heat-sensitive recording material was prepared according to the method described in (1).

Comparative Example 3 In Example 1, the electron accepting compound in Solution B was
Instead of using the developer composition prepared in Production Example 1,
A heat-sensitive recording material was prepared according to the method described in Example 1, except that 2,2-bis (4'-hydroxyphenyl) propane was used.

Comparative Example 4 A heat-sensitive recording material was produced in the same manner as in Example 1, except that the overcoat layer was not provided (ie, the C solution was not used).

Each of the heat-sensitive recording materials prepared in Examples 1 to 27 and Comparative Examples 1 to 4 had a Beck smoothness of 400 to 400.
After performing a super calender treatment so as to reach 500 seconds, evaluation was performed according to the following evaluation method. The results are shown in Table 3.

[Evaluation method of thermosensitive recording material] (Coloring sensitivity test) Each thermosensitive recording material was measured at 0.49 mj / d.
After color development at ot energy, the resulting color image density was measured using a Macbeth densitometer (TR-54 type). The larger the value, the better the color sensitivity.

(Storage Stability Test of Colored Image) Each heat-sensitive recording material was converted to a heat-sensitive recording material color-developing device (TH-PM manufactured by Okura Electric Co.
D) was used to form a color image having a color density of 0.9 as measured with a Macbeth densitometer (TR-524), and then subjected to a storage stability test. In the storage stability test, a plasticizer resistance test was performed, and the whiteness of the uncolored portion of each thermosensitive recording paper after the test was examined. The plasticizer resistance test was performed by winding a vinyl chloride wrap film (manufactured by Mitsubishi Plastics, Inc.) three times on a polypropylene pipe (40 mmΦ).
On top of that, sandwich the color-developing surface of the thermosensitive recording paper on the outside, further wrap a vinyl chloride wrap film three times on it, and leave it at 25 ° C for 4 days. It was measured using a densitometer, and the residual ratio of the color image was determined.

[0153] The larger the value, the better the storage stability of the color image.

(Writing implement test) A writing implement test was performed for each heat-sensitive recording material using a pencil (hardness H, manufactured by Mitsubishi Pencil Co.). ○ indicates that the writing can be performed smoothly and the density of the writing area is high, △ indicates that it is difficult to write without applying pressure, and that the density of the writing area is low. However, it is difficult to write, and the density of the writing part is very low.

(Touch Test) Ten heat-sensitive recording materials were handled by 10 persons who had handled general facsimile paper, and the touch with plain paper (Xerox paper PA-4) was compared. ○ indicates that 8 or more persons evaluated the same hand, Δ indicates that 6 to 7 persons evaluated the same hand, and × indicates that five persons or less evaluated the same hand Is represented.

[0156]

[Table 3]

[0157]

[Table 4] As is clear from Table 3, the heat-sensitive recording material of the present invention
Excellent color sensitivity, storage stability of color image (plasticizer resistance)
Is very excellent, and can be written with a writing instrument such as a pencil, and furthermore, it can be seen that it is a heat-sensitive recording material whose touch is close to that of plain paper.

Example 28 100 g of solution A prepared in Example 1, 100 g of solution B, and oil absorption
138ml / 100g calcium carbonate [Shiroishi Co., Ltd.
Industrial Callite KT] 100 g, 20% oxidized starch water
75 g of solution, 75 g of 20% aqueous polyvinyl alcohol solution
Were mixed and stirred to prepare a coating solution for the recording layer. The coating solution,
Fine paper (basis weight 50g / m^Two), The dry coating amount is 5.
5g / m Coated and dried to form a heat-sensitive recording layer
did. (2) Preparation of microcapsule dispersion liquid (D liquid)
Roxy-5'-methylphenyl) benzotriazole 3
g, xylylene diisocyanate and trimethylol pro
Bread (3: 1) adduct (Takeda Pharmaceutical, Takenate
D-110N, containing 25% ethyl acetate) 27 g
Dissolve the solution and use polyvinyl alcohol (Kuraray-21
TK homomixer in 80 g of 8% aqueous solution of 7)
(Model HV-M manufactured by Tokushu Kika Kogyo Co., Ltd.)
It was emulsified and dispersed so that the particle diameter became 2 μm. Then this milk
72 g of water is added to the dispersion and the mixture is stirred at 60 ° C. for 3 hours.
Polyurethane poly with UV absorber
Microcapsule dispersion with urea resin wall film
A liquid (D liquid) was prepared. (3) Formation of overcoat layer 200 g of microcapsule dispersion liquid (D liquid), acetoacetate
Tyl group modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Company,
Gosefimer Z-200) 10% aqueous solution 150
g, kaolin 15g, zinc stearate 30% aqueous dispersion
A mixture consisting of 6 g of the liquid and 30 g of water was stirred and mixed,
A coating solution for an overcoat layer was prepared. This coating solution
On the thermal recording layer, the dry coating amount is 5.0 g / m^TwoWill be
After being applied and dried, it is super calendered,
A heat-sensitive recording material was produced.

Examples 29 to 40 Combinations (combination numbers 2 to 13) of the electron-donating color-forming compound, the heat-fusible compound and the electron-accepting compound in Solution A shown in Table 1 were used. A heat-sensitive recording material was produced according to the method described in Example 28.

Example 41 In the preparation of the microcapsule dispersion liquid (D liquid) of Example 28, 2- (2'-methylphenyl) benzotriazole was replaced with 2- (2'-
A heat-sensitive recording material was prepared according to the method described in Example 28 except that 3 g of (hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole was used.

Example 42 In the preparation of the microcapsule dispersion liquid (D liquid) of Example 28, 2- (2′-hydroxyphenyl-5) -methylphenyl
A heat-sensitive recording material was prepared according to the method described in Example 28 except that 3 g of (hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole was used.

Example 43 In the preparation of the microcapsule dispersion liquid (D liquid) of Example 28, 2- (2'-hydroxyphenyl-5) -methylphenyl
Hydroxy-3'-dodecyl-5'-methylphenyl)
Example 28 except that 5 g of benzotriazole was used.
A heat-sensitive recording material was prepared according to the method described in (1).

Example 44 In preparation of the microcapsule dispersion liquid (D liquid) of Example 28, 2- [2'-hydroxyphenyl-5-methylphenyl) benzotriazole was replaced by 3- [2'-
[Hydroxy-4 '-(2 "-ethylhexyloxy) phenyl] benzotriazole was used in the same manner as in Example 28 except for using 8 g of the thermosensitive recording material.

Example 45 A microcapsule dispersion (solution E) prepared by the following method was used in place of the microcapsule dispersion (solution D) in forming the overcoat layer in Example 28. According to the method described in Example 28, a heat-sensitive recording material was produced. To 15 g of diisopropylnaphthalene, 2-
A solution in which 2 g of (2'-hydroxy-5'-methylphenyl) benzotriazole was dissolved was added to 20 g of a 5% aqueous solution of polyacrylic acid adjusted to pH 4.5, and TK was added.
The mixture was emulsified and dispersed using a homomixer (Model HV-M, manufactured by Tokushu Kika Kogyo Co., Ltd.). To this emulsified dispersion, 20 g of a 30% aqueous solution of a melamine-formaldehyde precondensate was added, and the mixture was stirred and reacted at 90 ° C. for 3 hours. A microcapsule dispersion liquid (liquid E) having a wall film was prepared.

Comparative Example 5 In Example 28, N- (4-hydroxyphenyl) -benzenesulfonamide was used instead of using the developer composition prepared in Production Example 1 as the electron accepting compound in the solution B. A thermosensitive recording material was prepared according to the method described in Example 28, except that was used.

Comparative Example 6 In Example 28, N- (4-hydroxyphenyl)-(4 ′) was used instead of using the developer composition prepared in Production Example 1 as the electron-accepting compound in the solution B. Example 2 except that (-methylbenzene) sulfonamide was used.
According to the method described in No. 8, a heat-sensitive recording material was produced.

Comparative Example 7 In Example 28, instead of using the developer composition prepared in Production Example 1 as the electron-accepting compound in the solution B, 2,2-bis (4′-hydroxyphenyl) was used. A heat-sensitive recording material was produced according to the method described in Example 28 except that propane was used.

Comparative Example 8 The procedure of Example 28 was repeated except that 2- (2′-hydroxy-5′-methylphenyl) benzotriazole was not used in preparing the microcapsule dispersion liquid (D liquid) of Example 28. According to the method described, a heat-sensitive recording material was produced. Each of the heat-sensitive recording materials prepared in Examples 28 to 45 and Comparative Examples 5 to 8 had a Beck smoothness of 400 to 500.
After performing the super calender treatment so that the time becomes seconds, evaluation was performed according to the following evaluation method, and the results are shown in Table 4.

[Evaluation of thermosensitive recording material] (Storage stability test of uncolored portion) The whiteness of the uncolored portion (background) immediately after the application of each thermosensitive recording material was measured using a color difference meter (Σ-80, manufactured by Nippon Denshoku). It measured using. In the storage stability test, a light fastness test was performed, and the whiteness of the uncolored portion of each heat-sensitive recording material after the test was examined. In the light resistance test, the coated surface of each heat-sensitive recording material was exposed to direct sunlight for two days, and then the whiteness of the uncolored portion was measured using a Macbeth densitometer (using a blue filter). The smaller the numerical value, the higher the whiteness and the better the storage stability of the uncolored portion. (Storage Stability Test of Colored Image) According to the method described above, a plasticizer resistance test of the colorized image of each heat-sensitive recording material was performed.

[0170]

[Table 5] As is clear from Table 4, the heat-sensitive recording material of the present invention
The storage stability (light resistance, plasticizer resistance) of the uncolored portion and the color image is very excellent.

Example 46 [Preparation of heat-sensitive recording material] (1) Formation of heat-sensitive recording layer 100 g of solution A and 100 g of solution B prepared in Example 1 and calcium carbonate having an oil absorption of 138 ml / 100 g [Shiraishi Kogyo Callite Co., Ltd.] KT] 100 g, 20% oxidized starch aqueous solution 75 g, 20% polyvinyl alcohol aqueous solution 75 g
Were mixed and stirred to prepare a coating solution for the recording layer. The coating liquid was coated with a synthetic paper having a thickness of 80 μm (Yupo FPG manufactured by Oji Yuka Synthetic Paper).
On top, applied so that the dry weight becomes 5.5 g / m ² ,
After drying, a super calender treatment was performed. (2) Formation of Intermediate Layer On the obtained thermosensitive recording layer, a coating liquid (F
Liquid) was applied such that the coating amount after drying was 4.0 g / m ² , dried, and then super-calendered to form an intermediate layer having a Beck smoothness of 5000 seconds. (F liquid composition) 10% aqueous solution of polyvinyl alcohol 800g Calcium carbonate 100g Water 100g ―――――――――――――――――――――――――――――― Total 1000g (3) Formation of overcoat layer An oligoester acrylate (T
g is 250 ° C or more, manufactured by Toa Gosei Chemical Co., Ltd., M-8030)
100 g and calcium carbonate 15 having an average particle size of 0.2 μm
g of the mixed solution was applied so that the coating amount after drying was 4.0 g / ╂, and treated with an electron curtain type electron beam irradiation device (CB: 150, manufactured by ESI) at an irradiation dose of 3 Mrad. Then, the resin component was cured to form an overcoat layer, thereby producing a thermosensitive recording material.

Examples 47 to 58 Using the combinations (combination numbers 2 to 13) of the electron-donating color-forming compound, the heat-fusible compound and the electron-accepting compound in solution A shown in Table 1 in solution A, were used. Thus, a heat-sensitive recording material was produced according to the method described in Example 46.

Example 59 In the formation of the recording layer of Example 46, instead of the synthetic paper having a thickness of 80 μm (made by Oji Yuka Synthetic Paper, YUPO FPG), 8
A heat-sensitive recording material was prepared according to the method described in Example 46 except that 0 g / m ² of paper was used.

Example 60 In the formation of the overcoat layer in Example 46, dipentaerythritol hexaacrylate (Tg after curing was 25%) was used instead of 100 g of the oligoester acrylate.
A heat-sensitive recording material was produced in accordance with the method described in Example 46, except that 100 g (0 ° C. or higher) was used.

Example 61 In the formation of the overcoat layer of Example 46, pentaerythritol triacrylate (Tg after curing was 250 ° C.) was used instead of 100 g of oligoester acrylate.
Above) A heat-sensitive recording material was prepared according to the method described in Example 46 except that 100 g was used.

Comparative Example 9 In Example 46, N- (4-hydroxyphenyl) -benzenesulfonamide was used as the electron accepting compound in the solution B, instead of using the developer composition prepared in Production Example 1. A thermosensitive recording material was prepared according to the method described in Example 46, except that was used.

Comparative Example 10 In Example 46, N- (4-hydroxyphenyl)-(4 ′) was used as the electron accepting compound in the solution B, instead of using the developer composition prepared in Production Example 1. Example 4 except that (-methylbenzene) sulfonamide was used.
According to the method described in No. 6, a heat-sensitive recording material was produced.

Comparative Example 11 In Example 46, instead of using the developer composition prepared in Production Example 1 as the electron-accepting compound in the solution B, 2,2-bis (4′-hydroxyphenyl) was used. A heat-sensitive recording material was produced according to the method described in Example 46 except that propane was used.

Comparative Example 12 A thermosensitive recording material was produced in the same manner as in Example 46 except that the overcoat layer was not provided. Each of the heat-sensitive recording materials prepared in Examples 46 to 61 and Comparative Examples 9 to 12 had a Beck smoothness of 40.
After performing a super calender treatment so that the time becomes 0 to 500 seconds, evaluation was performed according to the following evaluation method, and the results are shown in Table 5.

[Evaluation of Thermosensitive Recording Material] (Storage stability test of uncolored portion) The whiteness of the uncolored portion (background) immediately after the application of each thermosensitive recording material was measured using a color difference meter (Σ-80, manufactured by Nippon Denshoku). It measured using. In the storage stability test, a moist heat resistance test was performed, and the whiteness of the uncolored portion of each heat-sensitive recording material after the test was examined. Moisture / heat resistance test: 40 ° C, 90% R
After being left under the condition of H for 24 hours and 72 hours, the whiteness of each uncolored portion was measured using a color difference meter.
The larger the numerical value, the higher the whiteness and the better the storage stability of the uncolored portion.

(Storage Stability Test of Colored Image) Each of the heat-sensitive recording materials prepared in Examples and Comparative Examples was subjected to a Macbeth densitometer (TR-524 type) using a heat-sensitive recording material color developing device (TH-PMD manufactured by Okura Electric Co., Ltd.). ) Was used to form a color image having a color density of 0.9, followed by a storage stability test. In addition, the storage stability test performs a moisture heat resistance test,
The image storage stability of each heat-sensitive recording material after the test was examined. In the moist heat resistance test, the color image densities were measured using a Macbeth densitometer after standing for 24 hours and 72 hours at 40 ° C. and 90% RH, and the residual ratio of the color images was determined. The larger the value, the better the storage stability of the color image. In Table 5, A is 40 ° C., 90%
It shows the whiteness of the uncolored portion and the residual ratio of the color image after being left for 24 hours under the condition of RH. B is 40 ° C.
It shows the whiteness of the uncolored portion and the residual ratio of the color image after being left for 72 hours under the condition of 90% RH.

[0182]

[Table 6] As is clear from Table 5, the heat-sensitive recording material of the present invention
The storage stability (wet heat resistance) of the uncolored portion and the color image is very good.

[0183]

According to the present invention, it has become possible to provide a heat-sensitive recording material having excellent storage stability of an uncolored portion and a color image.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C07C 311/29 C07C 311/36 311/36 B41M 5/18 101E 101C (72) Inventor Masakatsu Nakatsuka Yokohama, Kanagawa 1190 Kasama-cho, Sakae-ku, Mitsui Chemical Co., Ltd. (72) Inventor Yoshimitsu Tanabe 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Prefecture Chemical Co., Ltd. F term (reference) 2H026 AA07 AA21 BB25 BB28 BB39 CC05 DD13 DD32 DD55 FF11 FF15 4H006 AA03 AB93

Claims (14)

[Claims] 1. A thermosensitive recording material comprising: a support, a thermosensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound, and a protective layer provided on the thermosensitive recording layer. The receptive compound contains at least one compound selected from the compounds represented by the general formula (1) and at least one compound selected from the compounds represented by the general formulas (2) and (3). Thermal recording material using a developer composition. Embedded image (Wherein X ₁ , X ₂ and X ₃ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group,
Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom or an alkyl group, and R _{1 to} R ₅ , R _{11 to} R ₁₅ , R _{21 to} R ₂₅ and R _{31 to} R
₃₅ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and further, R ₁ and R ₂ , R ₂
And R ₃ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₂₁ and R ₂₂ , R ₂₂ and R ₂₃ , R ₃₁ and R ₃₂ , or R ₃₂ and R ₃₃ , the mutually adjacent groups are bonded to each other And may form a carbocyclic aromatic ring together with the carbon atoms that are substituted) 2. At least one compound selected from the compounds represented by the general formulas (2) and (3) is added to 0.0100 parts by weight of the compound represented by the general formula (1).
2. The heat-sensitive recording material according to claim 1, which contains 1 to 10 parts by weight. 3. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording layer further contains a heat-fusible compound. 4. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording layer further contains an ultraviolet absorbent. 5. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording layer further contains a hindered phenol compound. 6. The heat-sensitive recording material according to claim 1, further comprising a binder in the heat-sensitive recording layer. 7. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording layer further contains a pigment. 8. The heat-sensitive recording material according to claim 7, wherein the pigment has an oil absorption of 50 ml / 100 g or more according to JIS K-5101. 9. The heat-sensitive recording material according to claim 1, further comprising an undercoat layer provided between the support and the heat-sensitive recording layer. 10. The heat-sensitive recording material according to claim 1, wherein the protective layer comprises an overcoat layer containing a water-soluble resin or a water-dispersible resin and a pigment as main components. 11. The heat-sensitive recording material according to claim 1, wherein the protective layer contains an ultraviolet absorbent. 12. The heat-sensitive recording material according to claim 11, wherein the ultraviolet absorbent is encapsulated in microcapsules. 13. A film formed from a water-soluble resin or a water-dispersible resin at 20 ° C. and 60% relative humidity (R).
The heat-sensitive recording material according to any one of claims 10 to 12, which is a resin having a tear strength of 1 kg / mm or more in H). 14. The protective layer according to claim 1, wherein the protective layer comprises an intermediate layer mainly composed of a water-soluble resin or a water-dispersible resin and an overcoat layer mainly composed of an ionizing radiation-curable resin. The heat-sensitive recording material described in Crab.