JP2000345067A - Developer composition and thermal recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal recording material which is excellent in coloring sensitivity and in storage stabilty of colored image by using a developer composition prepared by compounding a sulfonamide derivative having a phenolic hydroxy group with a sulfonic ester derivative having an amino group or a sulfonamide derivative having a sulfonic ester group. SOLUTION: This developer composition is prepared by compounding 100 pts.wt. compound of formula I with 0.01-10 pts.wt. ingredient comprising a compound of formula II and/or a compound of formula III. In the formulas, X1 to X3 are each H, a halogen, alkyl, alkoxy, or hydroxyl; and R1 to R5, R11 to R15, and R31 to R35 are each H, a halogen, alkyl, alkoxy, or aryl provided that two adjacent groups selectd from among combinations of R1 with R2, R2 with R3, R11 with R12, R12 with R13, R21 with R22, R22 with R23, R31 with R32, and R32 with R33 may be bonded to each other to form, together with carbon atoms to which they are bonded, a carbocyclic aromatic ring. The composition is incorporated into an electron-accepting compound contained in a thermal recording layer formed on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer composition and a heat-sensitive recording material containing the developer composition.

[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 (1993)). −13071
No.).

However, the heat-sensitive recording material has relatively low color-forming sensitivity and poor light stability of a color image, so that a high-performance heat-sensitive recording material is required.

At present, there is a demand for a heat-sensitive recording material which is excellent in color sensitivity and further excellent in storage stability of a color image.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel developer composition (particularly, a developer composition for a heat-sensitive recording material). Another object of the present invention is to provide a heat-sensitive recording material which is excellent in color sensitivity using the color developer composition and further excellent in storage stability of a color image.

[0007]

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) 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) A developer composition containing a compound of the type

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 substituted carbon atom.) 2) For 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 developer composition according to I, wherein the heat-sensitive recording material comprises a heat-sensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound on a support. A) a heat-sensitive recording material containing the developer composition according to 1) or 2); 4) a heat-sensitive recording material according to 3) further containing a heat-fusible compound in the heat-sensitive recording layer; 5) a heat-sensitive recording layer 3) or 4), further comprising an ultraviolet absorber; 6) The thermal recording according to any of 3) to 5) above, wherein the thermal recording layer further comprises a hindered phenol compound. 7) The heat-sensitive recording material according to any one of the above 3) to 6), further comprising a binder in the heat-sensitive recording layer; 8) The heat-sensitive recording layer further containing a pigment in the heat-sensitive recording layer
7) The heat-sensitive recording material according to any one of 9), 9) the pigment has an oil absorption of 5 according to JIS K-5101 method.
8) The heat-sensitive recording material according to 8), which is 0 ml / 100 g or more; 10) The heat-sensitive recording material according to any of 3) to 9), further comprising an undercoat layer provided between the support and the heat-sensitive recording layer. Things.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The developer composition of the present invention comprises 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) Which comprises the compound of

[0010]

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)

In the compounds represented by the general formulas (1), (2) and (3), X ₁ , X ₂ and X ₃
Represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group, preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group having 1 to 6 carbon atoms (eg, Methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group), alkoxy group having 1 to 6 carbon atoms ( For example, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group), a hydroxyl group, and more preferably a hydrogen atom, halogen An atom or an alkyl group having 1 to 4 carbon atoms, more preferably
It is a hydrogen atom or a halogen atom.

In the compounds represented by the general formulas (1), (2) and (3), Z ₁ , Z ₂ and Z ₃
Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group), and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the compounds represented by the general formulas (1), (2) and (3), R _{1 to} R ₅ , R _{11 to} R
₁₅ , R _{21 to} R ₂₅ and R _{31 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, preferably a hydrogen atom, a halogen atom (for example,
A fluorine atom, a chlorine atom, a bromine 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, 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, cyclohexyloxy group), aryl group having 6 to 10 carbon atoms (for example, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4- Ethylphenyl group, 3-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-sec-butylphenyl group, 4-tert
-Butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl 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-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 2,4-dichlorophenyl group, 2,5 -Dichlorophenyl group, 2-
A methoxy-4-methylphenyl group, a 2-methyl-4-methoxyphenyl group, a 2,4-dimethoxyphenyl group,
3,4-dimethoxyphenyl group, 3,5-diethoxyphenyl 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, more preferably a hydrogen atom or 1 to 4 carbon atoms.
4 alkyl group.

Further, general formulas (1), (2),
In the compound represented by the general formula (3), R₁And R_Two, R_Two
And R_Three, R₁₁And R₁₂, R₁₂And R₁₃, R_{twenty one}And R_{twenty two}, R_{twenty two}When
R_{twenty three}, R ₃₁And R₃₂Or R₃₂And R₃₃Each 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 hydroxyl group is substituted at the 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.

[0016]

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.

Example 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 acid ester derivative having an amino group, and the substitution position of the sulfonic acid ester is 4-position, 3-position or 2-position with respect to the amino group, 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.

[0020]

Embedded image [Wherein X ₂ , Z ₂ and R _{11 to} R ₁₅ have the same meaning as in 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.

Example 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) sulfonic acid ester 2-11. (4-Aminophenyl)-(4′-n-hexylbenzene) sulfonic acid ester 2-12. (4-aminophenyl)-(4′-cyclohexylbenzene) sulfonic acid ester 2-13. (4-aminophenyl)-(3 ′, 4′-dimethylbenzene) sulfonic acid ester 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) sulfonic acid ester 2-18. (4-aminophenyl)-(4'-n-butoxybenzene) sulfonic acid ester 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) sulfonic acid ester 2-45. (3-Aminophenyl)-(4′-isopropylbenzene) sulfonic acid ester 2-46. (3-Aminophenyl)-(4′-n-butylbenzene) sulfonic acid ester 2-47. (3-aminophenyl)-(4′-tert
-Butylbenzene) sulfonic acid ester 2-48. (3-Aminophenyl)-(4′-n-pentylbenzene) sulfonic acid ester 2-49. (3-Aminophenyl)-(4′-n-hexylbenzene) sulfonic acid ester 2-50. (3-Aminophenyl)-(4′-cyclohexylbenzene) sulfonic acid ester 2-51. (3-Aminophenyl)-(3 ′, 4′-dimethylbenzene) sulfonic acid ester 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) sulfonic acid ester 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),
It is a sulfonamide derivative having a sulfonate group, and the substitution position of the sulfonate 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.

[0024]

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) sulfonamide 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] -(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) phenyl] -(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'-methylbenzenesulfonyl) Oxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-39. Nn-butyl-N- [4- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-40.N-methyl-N- [4- (1'-naphthalene) Sulfonyloxy) 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]-(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-pentyloxybenzenesulfonyloxy) phenyl]-(4 "-n-pentyloxybenzene) sulfonamide 3-60.N- [3- (4'-n-hexyloxybenzene) Sulfonyloxy) 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] -benzene Sulfonamide 3-71.N- [4-hydroxy-3- (benzenesulfonyloxy) phenyl] -benzenesulfonamide 3-72.N- [4-hydroxy-3- (4'-methylbenzenesulfonyloxy) 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] -benzenesulfonamide 3-77. N-ethyl-N- [3- (4'-methoxybenzenesulfonyloxy) phenyl]-(4 "-methoxybenzene) sulfonamide 3-78.N-isopropyl-N- [3- (4'-methylbenzenesulfonyl) Oxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-79. Nn-butyl-N- [3- (4'-methylbenzenesulfonyloxy) phenyl]-(4 "-methylbenzene) sulfonamide 3-80.N-methyl-N- [3- (1'-naphthalene Sulfonyloxy) 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 "-methoxybenzene)
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'-methylbenzenesulfonyl) Oxy) 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. A. 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).

[0027]

Embedded image [In the formula, X ₁ , Z ₁ and R _{1 to} 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. A. 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).

[0029]

Embedded image [Wherein X ₂ , Z ₂ and R _{11 to} 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 method known per se [for example, JP-A-57-200].
No. 340, J. A. 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

[0031]

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 developer composition of the present invention comprises at least one compound represented by the general formula (1) and at least one compound selected from the compounds represented by the general formulas (2) and (3). This is a developer composition containing the following compounds (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 so much. Preferably, the amount of the compound represented by the general formula (1) is 100 parts by weight. , 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.

In the heat-sensitive recording material of the present invention, at least one compound represented by the general formula (1) and a compound represented by the general formulas (2) and (3) are used as the electron-accepting compound. The developer composition A contains at least one compound selected from the group consisting of:

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.
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, b) when producing the compound represented by the general formula (1), depending on the reaction conditions, the compound represented by the general formula (2) or / and the general formula (3) is formed as a by-product. (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 b)
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) and 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).

In 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 use amount of the developer composition A of the present invention as an electron-accepting compound is not particularly limited. 50 to 700 parts by weight
It is desirable to use about 100 parts 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 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 compounds, spiro compounds, and fluorene compounds,
More preferred are fluoran compounds, and among them, fluoran compounds represented by the general formula (A) are preferred.

[0047]

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, 3 -[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.

The diarylmethane compounds include, for example, 4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine,
N-2,4,5-trichlorophenylleuco auramine and the like. Rhodamine-lactam compounds include
For example, rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, rhodamine-B
-(4-chloroanilino) lactam and the like.

As the thiazine compound, 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 compound include, for example, 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 other electron accepting compounds in combination. In this case, the ratio of the developer composition A to the total electron-accepting compound 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-methylphenylsulfonyl) 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-cyclohexyloxycarbonylaminosalicylic 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, 4-tert-butylbenzoic acid, 2-
Benzoylbenzoic acid, 2- (4'-chlorobenzoyl)
Benzoic acid, 4-nitrobenzoic acid, 4-chlorobenzoic acid,
Organic acid derivatives such as 4-trifluoromethylbenzoic acid, 4-formylbenzoic acid, 4-cyanobenzoic acid, and stearic acid, and metal salts of these organic acid derivatives (for example, metals such as nickel, zinc, aluminum, and calcium) Salts), for example, zinc thiocyanate antipyrine complex,
Complexes such as molybdate acetylacetone complex, for example, N, N'-diphenylthiourea, N, N'-di (3
-Trifluoromethylphenyl) thiourea, N, N'-
Di (3-chlorophenyl) thiourea, 1,4-di (3 ′
Organics such as urea derivatives such as -chlorophenyl) -3-thiosemicarbazide, N-phenyl-N '-(4-methylphenylsulfonyl) urea, and 4,4'-bis (4 "-methylphenylsulfonylaminocarbonylamino) diphenylmethane Examples of the electron-accepting compound include, but are not limited to, inorganic electron-accepting compounds such as acid clay, attapulgite, activated clay, aluminum chloride, zinc chloride, and zinc bromide. May be used in combination.

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 color-forming compound. It is desirable to use parts by weight.

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, the developer composition A of the present invention, and if desired,
The heat fusible compound, etc., together or separately, usually mixed with a ball mill, sand mill (vertical type, horizontal type), attritor, colloidal mill, etc., and crusher, usually 3 μm
In the following, preferably, the dispersion is pulverized to a particle size of 2 μm or less, mixed and prepared to prepare a coating liquid for a heat-sensitive recording layer.

In the coating solution 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 used is not particularly limited.
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 or more. / 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 absorber 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 part 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, and ferric chloride.

The hindered phenol compound is preferably a phenol derivative in which at least one ortho position of the phenolic hydroxyl group is substituted with a branched alkyl group. For example, 2,6-diisopropyl-4-methylphenol, 2,6-diphenol -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 to be used is not particularly limited.
It is desirable to use about part 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).

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. The coating amount of the heat-sensitive recording layer is not particularly limited, but is generally 1.5 to 12 in terms of dry weight.
g / m ² approximately, preferably prepared in about 2 to 10 g / m ^2.

Examples of the support include, but are not particularly limited to, paper (eg, high-quality paper, art paper, coated paper, oil-resistant paper, recycled paper), and plastic (eg, polyethylene, polypropylene, polyester, polystyrene, Nylon) sheets, synthetic papers, plastic-laminated papers, or composite sheets or nonwoven sheets combining these, as well as molded articles and metal deposits are used.

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 developing sensitivity can be further increased, and the dot reproducibility during printing can be increased. Generally, the undercoat layer (undercoat layer) contains a pigment or a synthetic resin.

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 made 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, the coating liquid for the undercoat layer may contain a releasing agent, a water-proofing agent, a sizing agent (eg, alkenyl succinate, alkyl ketene dimer, rosin compound), a wax (eg, 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 with 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).

[0091]

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) was 2.95%, and this composition 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] (Composition A) Electron-donating color-forming compound 10 g Heat-fusible compound 20 g 5% methylcellulose aqueous solution 10 g80 g of water  Total 120g (B-solution composition) Electron-accepting compound 20g 5% methylcellulose aqueous solution 10g100g of water  130g in total

The above liquids A and B were each dispersed by a sand mill so that the average particle diameter became 1.5 μm, to prepare dispersions. Next, solution A 120 g, solution B 130 g, 30
10 g of 10% paraffin wax, 170 g of an aqueous solution of 10% polyvinyl alcohol (Kuraray PVA-105), and 25 g of calcium carbonate [Shiraishi Kogyo Kallite KT] having an oil absorption of 138 ml / 100 g were mixed and stirred to prepare a coating solution for the recording layer. Prepared. The coating liquid was applied on a high-quality paper (basis weight: 50 g / m ² ) so as to have a dry coating amount of 5.5 g / m ^2, and dried to prepare a heat-sensitive recording material.

Examples 2 to 13 In Example 1, an electron-donating color-forming compound in Solution A was used.
A coating liquid for a recording layer was prepared by the method described in Example 1 except that each of the compounds shown in Table 1 was used as the heat-fusible compound, to prepare a heat-sensitive recording material.

[0097] 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 adipic acid diphenyl ester, 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, thermofusible compound j, 4,4′-diallyloxydiphenylsulfone, thermofusible compound k, terephthalic acid dimethyl ester, thermofusible compound l, 1,2 -Bis (3 ', 4'-dimethylphenyl) ethane.

[0098]

[Table 1]

Examples 14 to 23 In Example 1, the electron accepting compound in the solution B was
Instead of using the developer composition prepared in Production Example 1,
Example 1 except that the developer composition shown in Table 2 was used.
A coating solution for a recording layer was prepared by the method described in (1) to prepare a heat-sensitive recording material. In addition,% in a table | surface represents the weight% in a composition.

[0100]

[Table 2]

Example 24 In Example 1, instead of using 25 g of calcium carbonate having an oil absorption of 138 ml / 100 g [Shiraishi Kogyo Callite KT], calcium carbonate having an oil absorption of 60 ml / 100 g [Shiraishi Kogyo Kallite Co., Ltd.] was used. SA], except that 25 g was used, a coating solution for a recording layer was prepared by the method described in Example 1 to prepare a thermosensitive recording material.

Example 25 Instead of using 25 g of calcium carbonate [Shiraishi Kogyo Kallite KT] having an oil absorption of 138 ml / 100 g in Example 1, amorphous silica having an oil absorption of 70 ml / 100 g [Mizusawa Co., Ltd.] A coating solution for a recording layer was prepared by the method described in Example 1 except that 25 g of Chemical P553A] was used to prepare a thermosensitive recording material.

Example 26 Instead of using 25 g of calcium carbonate having an oil absorption of 138 ml / 100 g [Shiraishi Kogyo Callite KT] in Example 1, amorphous silica having an oil absorption of 170 ml / 100 g [Mizusawa Co., Ltd.] A coating solution for a recording layer was prepared in the same manner as in Example 1 except that 40 g of Chemical P527 was used to prepare a thermosensitive recording material.

Example 27 Instead of using 25 g of calcium carbonate having an oil absorption of 138 ml / 100 g [Shiraishi Kogyo Callite KT] in Example 1, amorphous calcium silicate having an oil absorption of 145 ml / 100 g [(Co. Mizusawa Chemical's P832] 20
Except for using g, by the method described in Example 1,
A coating solution for a recording layer was prepared to prepare a heat-sensitive recording material.

Example 28 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 ). A heat-sensitive recording material was produced by the method described in Example 1. [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 100% 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 liquid on a high-quality paper (basis weight 50 g / m ² ) so as to have a dry coating amount of 7.0 g / m ² ,
The paper provided with the undercoat layer was produced by performing a super calender treatment.

Example 29 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 ). A heat-sensitive recording material was produced by the method described in Example 1. [Preparation of paper provided with undercoat layer] Average particle size is 1.0 μm
In a 400 g 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 sufficiently stirred to prepare a coating liquid for an undercoat layer. The coating solution is applied on a high quality paper (basis weight 50 g / m ² )
After coating and drying to a thickness of μm, a super calender treatment was performed to produce a paper provided with an undercoat layer.

Example 30 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 according to the method described in Example 1 except that 8 g of the recording layer was used to prepare a thermosensitive recording material.

Example 31 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 coating solution for a recording layer was prepared according to the method described in Example 1, except that 8 g of benzotriazole was used, to prepare a thermosensitive recording material.

Example 32 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 4 g of 1,4-bis (4′-hydroxycumyl) benzene
A heat-sensitive recording material was prepared by preparing a coating solution for a recording layer according to the method described in Example 1, except for using.

Example 33 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. According to the method described in (1), a coating solution for a recording layer was prepared to prepare a heat-sensitive recording material.

Example 34 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′-isopropoxydiphenyl sulfone were used, According to the method described in Example 1, a coating liquid for a recording layer was prepared, and a thermosensitive 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,
Except that N- (4-hydroxyphenyl) -benzenesulfonamide was used, a coating solution for a recording layer was prepared according to the method described in Example 1 to prepare a thermosensitive recording material.

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,
Except that N- (4-hydroxyphenyl)-(4'-methylbenzene) sulfonamide was used, a coating solution for a recording layer was prepared according to the method described in Example 1 to prepare a heat-sensitive recording material.

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 coating solution for a recording layer was prepared according to the method described in Example 1, except that N- (3-hydroxyphenyl)-(4′-methylbenzene) sulfonamide was used, to prepare a thermosensitive recording material. For each of the heat-sensitive recording materials produced in the above Examples and Comparative Examples, the Beck smoothness was 400 to 50.
After performing a super calender treatment so that the time becomes 0 second, 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)
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 subjected to a heat-sensitive recording material coloring device (TH-PM manufactured by Okura Electric Co., Ltd.).
D) was used to form a color image having a color density of 1.0 as measured with a Macbeth densitometer (TR-524), and then subjected to a storage stability test. In the storage stability test, a light resistance test was performed, and the storage stability of a color image of each heat-sensitive recording material after the test was examined. In the light fastness test, a fluorescent lamp (20,000 lux) was applied to the colored image surface of the thermosensitive recording paper for 72 hours.
After irradiation for a period of time, the density of the color image was measured using a Macbeth densitometer, and the residual ratio of the color image was determined.

[0117]

(Equation 1) The larger the value, the better the storage stability of the color image.

[0118]

[Table 3]

[0119]

[Table 4]

As is clear from Table 3, the heat-sensitive recording material using the developer composition of the present invention as an electron-accepting compound was compared with the heat-sensitive recording material prepared using a conventional electron-accepting compound. Therefore, the color sensitivity and the storage stability of the color image are excellent.

[0121]

According to the present invention, it is possible to provide a heat-sensitive recording material excellent in color sensitivity and storage stability of a color-formed image, and a developer composition suitable for an electron-accepting compound for the heat-sensitive recording material. Became.

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) B41M 5/18 111 (72) Inventor Masakatsu Nakatsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Chemicals Co., Ltd. (72) Invention Person Yoshimitsu Tanabe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Jotaro Kurita 1190 Kasama-cho, Sakae-ku, Yokohama-shi Kanagawa Prefecture F-term in Mitsui Chemicals Co., Ltd. DD32 DD45 DD53 FF01 FF13 4H056 BA02 BB05 BB15 BF02F BF26F BF27F BF28E BF28F FA03

Claims (10)

[Claims] 1. A composition comprising 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). 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 100 parts by weight of the compound represented by the general formula (1) in an amount of 0.0
2. The developer composition according to claim 1, which contains 1 to 10 parts by weight. 3. A heat-sensitive recording material comprising a support having thereon a heat-sensitive recording layer containing an electron-donating color-forming compound and an electron-accepting compound. Heat-sensitive recording material containing an agent composition. 4. The heat-sensitive recording material according to claim 3, wherein the heat-sensitive recording layer further contains a heat-fusible compound. 5. The heat-sensitive recording material according to claim 3, wherein the heat-sensitive recording layer further contains an ultraviolet absorber. 6. The heat-sensitive recording material according to claim 3, wherein the heat-sensitive recording layer further contains a hindered phenol compound. 7. The heat-sensitive recording material according to claim 3, wherein the heat-sensitive recording layer further contains a binder. 8. The heat-sensitive recording material according to claim 3, wherein the heat-sensitive recording layer further contains a pigment. 9. The heat-sensitive recording material according to claim 8, wherein the pigment has an oil absorption of 50 ml / 100 g or more according to JIS K-5101. 10. The method according to claim 1, further comprising the step of:
The heat-sensitive recording material according to any one of claims 3 to 9, further comprising an undercoat layer.