JP2002357881A - Heat developable photosensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material ensuring little fog in raw stock preservation, hardly causing deterioration of contrast and density and unevenness in development in raw stock preservation and to provide a processing method for the heat developable photosensitive material. SOLUTION: In the heat developable photosensitive material having an organic silver salt, silver halide and a reducer on one side of the base, a hardener and a compound of the formula Rf<o> -(O-Rf')n1 -L'-X'm1 or [(Rf"O)n2 -(PFC)-CO- Y]k -L"-X"m2 are contained on the side of the base with the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material and a method for processing the photothermographic material. The present invention relates to a photothermographic material and a processing method for the photothermographic material, which hardly occur.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As this technique, for example, US Pat.
Nos. 52,904, 3,487,075 and D.I. "Dry Silver Photographic" by Morgan
Materials) "(Handbook of I
Managing Materials, MarcelDe
kker, Inc. 48, 1991), a photothermographic material containing an organic silver salt, photosensitive silver halide particles, a reducing agent and a binder on a support is known.

[0004] The photothermographic materials described above have a problem in raw storability, particularly at high temperatures, because a reducing agent is contained in the material. Also, since no fixing process is performed after thermal development,
There is a problem that fog increases with time.

As described above, in the photothermographic material, improvement of the above problems has been desired.

Since the above photothermographic material contains a reducing agent in the material, particularly in the case of a photothermographic material containing a high contrast agent, fogging occurs during storage for a long time,
There has been a problem that softening, a decrease in density, and unevenness in development are likely to occur.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to reduce fog during raw storage, hardly cause softening and lowering of the density, and cause uneven development during raw storage. An object of the present invention is to provide a photothermographic material and a processing method for the photothermographic material, which hardly occur.

[0008]

The above object of the present invention is achieved by the following constitution.

1. In a photothermographic material having an organic silver salt, silver halide and a reducing agent on one side of a support,
A photothermographic material comprising a contrast agent and a compound represented by formula (1) or (2) on a support having silver halide.

[0010] 2. In a photothermographic material having an organic silver salt, silver halide and a reducing agent on one side of a support,
A photothermographic material comprising a contrast agent and a compound represented by formula (3) on a support having silver halide.

3. The above-mentioned high contrast agent has the general formula (N-
(3) The photothermographic material as described in (1) or (2) above, which is a compound represented by (N-2) or (N-3).

4. When the photothermographic material is subjected to thermal development processing by a thermal developing machine, the surface on the side having silver halide is brought into contact with the roller to drive the roller, and is opposite to the side having silver halide with respect to the support. 4. The photothermographic material according to any one of the above items 1 to 3, wherein the photothermographic material is subjected to a heat development process by bringing the surface on the side thereof into contact with a smooth surface, sliding the surface, and performing heat development.

5. 5. The photothermographic material according to the item 4, wherein the transport speed at the time of the transport and the thermal development is 22 to 40 mm / sec.

6. 4. When the photothermographic material according to 1, 2, or 3 is thermally developed by a thermal developing machine, the surface on the side having silver halide is brought into contact with a roller to drive the roller, and to the support. A method for processing a photothermographic material, wherein the surface opposite to the side having silver halide is brought into contact with a smooth surface, slid and conveyed, and subjected to heat development.

[0015] 7. 7. The method for processing a photothermographic material according to the item 6, wherein the transport speed at the time of the transport and the thermal development is 22 to 40 mm / sec.

Hereinafter, the present invention will be described in detail. The compound represented by the general formula (1), the compound represented by the general formula (2) and the compound represented by the general formula (3) according to the present invention will be described.

First, the compound represented by formula (1) will be described. In the general formula (1), Rf ° represents an alkyl group, an aryl group, or an alkenyl group containing at least one fluorine atom. Rf 'represents an alkylene group containing at least one fluorine atom. L '
Represents a mere bond or a divalent linking group, and X ′ represents a hydroxy group, an anionic group or a cationic group. n1
And m1 each represent an integer of 1 or more.

Rf ° represents an alkyl group, an aryl group, or an alkenyl group containing at least one fluorine atom, and preferably has 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 12 carbon atoms. It is preferably from 3 to 7.

Rf 'represents an alkylene group containing at least one fluorine atom, and preferably has 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms,
Particularly, it is preferably 2 or 3. Also, (OR
f ′) _n1 is, for example, (O-Rf1 ′) _k − (O−
Rf2 ′) _l (where k + 1 = n1) may be an aggregate of different (O−Rf ′).

Each of n1 and m1 is an integer of 1 or more. Preferably, n1 is 1 or more and 10 or less, and m1 is 1 or more and 3 or less.

L 'represents a simple bond or a divalent linking group, preferably an alkylene group, an arylene group, a divalent linking group containing a hetero atom, or the like.

X 'represents a hydroxy group, an anionic group or a cationic group, wherein the anionic group is preferably a carboxy group, a sulfonic acid group, a phosphoric acid group or the like, and the counter cation is a sodium ion, a potassium ion or the like. Alkali metal ions, ammonium ions and the like are preferred. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like.

Preferred examples of the compound represented by formula (1) which can be used in the present invention are shown below, but the present invention is not limited thereto.

The following compounds are mentioned as examples of the anionic type.
I can do it. (1) -1. C_FiveF₁₁− (O-CF_Two) -O-PO (ON
a)_Two (1) -2. HC₆F₁₂− (O-CF_Two) -O-PO (O
Na)_Two (1) -3. C₈F₁₇− (O-CF_Two) -O-PO (ON
a)_Two (1) -4. C_TenF_{twenty one}− (O-CF_Two) -O-PO (O
Na)_Two (1) -5. C₁₂F_{twenty five}− (O-CF_Two) -O-PO (O
Na)_Two (1) -6. C_ThreeF₇− (OC_TwoF_Four) -O-PO (ON
a)_Two (1) -7. C_FourF₉− (OC_TwoF_Four) -O-PO (ON
a)_Two (1) -8. C_FiveF₁₁− (OC_TwoF_Four) -O-PO (O
Na)_Two (1) -9. HC₆F₁₂− (OC_TwoF_Four) -O-PO
(ONa)_Two (1) -10. C₇F₁₅− (OC_TwoF_Four) -O-PO
(ONa)_Two (1) -11. C₉F₁₉− (OC_TwoF_Four) -O-PO
(ONa)_Two (1) -12. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-PO
(ONa)_Two (1) -13. C_ThreeF₇− (O-CF_Two)₆-O-PO (O
Na)_Two (1) -14. C_FourF₉− (O-CF_Two)₆-O-PO (O
Na)_Two (1) -15. C_FiveF₁₁− (O-CF_Two)_Five-O-PO
(ONa)_Two (1) -16. HC₆F₁₂− (O-CF_Two)_Three-O-PO
(ONa)_Two (1) -17. C_ThreeF₇-[O- (CF_Two)_Three] -COON
a (1) -18. C_FourF₉-[O- (CF_Two)_Three] -COON
a (1) -19. C_FiveF₁₁-[O- (CF_Two)_Three] -COO
Na (1) -20. HC₇F₁₄-[O- (CF_Two)_Three] -O-
CH (COONa)_Two (1) -21. C₈F₁₇-[O- (CF_Two)_Three] -OC
H (COONa)_Two (1) -22. C_ThreeF₇-[O- (CF_Two)_Five] -COON
a (1) -23. C_FourF₉-[O- (CF_Two)_Five] -COON
a (1) -24. C_FiveF₁₁-[O- (CF_Two)_Five] -COO
Na (1) -25. C₇F₁₅-[O- (CF_Two)_Five] -COO
Na (1) -26. C_ThreeF₇− (OC_TwoF_Four)_Five-COONa (1) -27. C_FourF₉− (OC_TwoF_Four)_Two-COONa (1) -28. C_FiveF₁₁− (OC_TwoF_Four)_Two-COONa (1) -29. HC₇F₁₄− (OC_TwoF_Four)_Two-COON
a (1) -30. C₉F₁₉− (OC_TwoF_Four)_Two-COONa (1) -31. C_TwoF_Five− (OC_TwoF_Four)_Three-COONa (1) -32. C_TwoF_Five− (OC_TwoF_Four)_Five-COONa (1) -33. C_ThreeF₇− (OC_TwoF_Four)_Four-COONa (1) -34. C_FourF₉− (OC_TwoF_Four)_Three-COONa (1) -35. C_FiveF₁₁− (OC_TwoF_Four)_Three-NHCOC
H (COONa)_Two (1) -36. HC₆F₁₂− (OC_TwoF_Four)_Three-NHCO
CH (COONa)_Two (1) -37. C_FourF₉− (OC_TwoF_Four)_Two− (OC
F_Two) COONa (1) -38. C_FiveF₁₁− (OC_TwoF_Four)_Two− (O-CF
_Two) COONa (1) -39. C₇F₁₅− (OC_TwoF_Four)_Two− (O-CF
_Two) COONa (1) -40. C_FourF₉− (O-CF_Two)-[O- (C
F_Two)_Five] -COOK (1) -41. C_FiveF₁₁− (O-CF_Two)-[O- (CF
_Two)_Five] -COOK (1) -42. HC₆F₁₂− (O-CF_Two)-[O- (C
F_Two)_Five] -COOK (1) -43. C_FourF₉− (OC_TwoF_Four)_Five-[O- (C
F_Two)_Three] -COOK (1) -44. C_FiveF₁₁− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK (1) -45. C₆F₁₃− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK (1) -46. C₁₂F_{twenty five}− (O-CF_Two) -O-SO_ThreeN
a (1) -47. C₇F₁₅− (OC_TwoF_Four) -OC_ThreeH₆−
SO_ThreeNa (1) -48. C_FourF₉− (O-CF_Two)₆-O-SO_ThreeN
a (1) -49. HC_FiveF_Ten− (O-CF_Two)_Five-OC_ThreeH₆
-SO_ThreeNa (1) -50. HC₆F₁₂− (O-CF_Two)_Three-O-SO_Three
Na (1) -51. C_FiveF₁₁− (OC_TwoF_Four)_Two-OC_ThreeH₆−
SO_ThreeNa (1) -52. C₇F₁₅− (OC_TwoF_Four)_Two-O-SO_Three
Na (1) -53. C_ThreeF₇− (OC_TwoF_Four)_Four-OC_ThreeH₆−
SO_ThreeNa (1) -54. C_FourF₉− (OC_TwoF_Four)_Three-O-SO_ThreeN
a (1) -55. HC_FiveF_Ten− (OC_TwoF_Four)_Three-OC_ThreeH₆
-SO_ThreeNa (1) -56. C_FiveF₁₁− (O-CF_Two)-[O- (CF
_Two)_Five] -O-SO_ThreeNa (1) -57. C_FourF₉− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -O-SO_ThreeNa (1) -58. (HCF_Two)_ThreeC- (OC_TwoF_Four)_Three-O
-SO_ThreeNa (1) -59. (CF_Three)_TwoCFCF_TwoCF_Two− (O-CF
_Two)_Five-OC_ThreeH₆-SO _ThreeNa (1) -60. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-SO_Three
Examples of the Na cation type include the following compounds.

(1) -61. C_FourF₉− (OC_TwoF_Four)_Three
-NHCOC_ThreeH₆-N⁺(CH_Three)_Three・ Br^- (1) -62. C_FiveF₁₁− (OC_TwoF_Four)_Two-NHCOC
_ThreeH₆-N⁺(CH_Three)_Three・ Br^- (1) -63. HC₆F₁₂− (OC_TwoF_Four)_Two-NHCO
C_ThreeH₆-N⁺(CH_Three) _Three・ Br^- (1) -64. C_FourF₉− (OC_TwoF_Four)_Three-OCH_Two-N
⁺(CH_Three)_Two(C_TwoH_FourOH) ・ Br^- (1) -65. C_FiveF₁₁− (OC_TwoF_Four)_Two-OCH_Two−
N⁺(CH_Three)_Two(C_TwoH_FourOH) ・ Br^- (1) -66. HC₆F₁₂− (OC_TwoF_Four)_Two-OCH_Two
-N⁺(CH_Three)_Two(C_TwoH_FourOH), Br^- (1) -67. C_FiveF₁₁− (O-CF_Two)-(OC
_TwoF_Four) -NHCOC_ThreeH₆-N⁺(CH_Three)_Three・ Br^- (1) -68. (CF_Three)_ThreeC- (OC_TwoF_Four)_Three-OC
H_Two-N⁺(CH_Three)_Two(C_TwoH_FourOH) ・ Br^- Examples of the nonionic type include the following compounds.

(1) -69. _{C 12 F 25 - (O-} CF 2)
-OH (1) -70. _{C 7 F 15 - (O-} C 2 F 4) -OH (1) -71. _{C 4 F 9 - (O-} CF 2) 6 -OC 3 H 6 -O
H (1) -72. _{C 5 F 11 - (O-} CF 2) 5 -OC 3 H 6 -
OH (1) -73. _{HC 6 F 12 - (O-} CF 2) 3 -OH (1) -74. _{C 5 F 11 - (O-} C 2 F 4) 2 -OC 3 H 6 -
OH (1) -75. _{C 7 F 15 - (O-} C 2 F 4) 2 -OC 3 H 6 -
OH (1) -76. _{C 3 F 7 - (O-} C 2 F 4) 4 -OC 3 H 6 -
OH (1) -77. _{HC 4 F 8 - (O-} C 2 F 4) 3 -O-C
_{(C 2 H 4 OH) 3} (1) -78. _{C 5 F 11 - (O-} C 2 F 4) 3 -OC 3 H 6 -
OH (1) -79. _{C 5 F 11 - (O-} CF 2) - [O-(CF
₂ ) ₅ ] -OH (1) -80. _{C 4 F 9 - (O-} C 2 F 4) 2 - [O-(C
F _{2) 3]} -OH (1) -81. _{(CF 3) 3 C- (O} -C 2 F 4) 3 -OH (1) -82. (HCF ₂ ) ₂ CFCF ₂ CF _2- (OC
_{F 2) 5 -OH (1)} -83. C ₁₁ F ₂₃ - The synthesis method of _{(O-C 2 F 4)} 4 OH The fluorine-based surfactant may be Kohyo No. 10-500950, the Nos. 11-504360 reference.

The fluorine-based surfactant of the present invention preferably has a total of 7 or more carbon atoms to which a fluorine atom is bonded, particularly preferably 8 to 20.

The compound represented by formula (2) will be described. In the general formula (2), Rf ″ represents a perfluoroalkyl group having 1 to 4 carbon atoms, and n2 represents 1
Represents an integer of from 5 to 5. (PFC) represents a perfluorocycloalkylene group. Y represents a linking group containing an oxygen atom or a nitrogen atom, L ″ represents a mere bond or a divalent linking group, and X ″ represents a water-containing group containing an anionic group, a cationic group, a nonionic group or an amphoteric group. Represents a solubilized polar group. k represents an integer of 1 to 3, and m2 represents an integer of 1 to 5.

(PFC) represents a perfluorocycloalkylene group, and specific examples include a perfluorocyclooctylene group, a perfluorocycloheptylene group, a perfluorocyclohexylene group and a perfluorocyclopentylene group. .

L ″ represents a simple bond or a divalent linking group, and the linking group is a substituted or unsubstituted alkylene (eg, ethylene group, propylene group, isobutylene group, etc.), arylene (eg, phenylene group) Group), a combination of an alkylene group and an arylene group (eg, a xylylene group), an oxydialkylene group (eg, CH ₂ CH ₂ OC)
H ₂ CH ₂ group), thiodialkylene group (eg, CH ₂
CH ₂ SCH ₂ CH ₂ group etc.) and generally a divalent linking group.

X ″ is a water-solubilizing polar group containing an anionic group, a cationic group, a nonionic group or an amphoteric group (betaine type), or an arbitrary combination thereof.

Typical anionic groups include CO
₂ H, CO ₂ M, SO ₃ H, SO ₃ M, OSO ₃ H, OSO ₃
M, (OCH ₂ CH ₂ ) OSO ₃ M, OPO (OH) ₂ , OPO (OM) _{2 and the} like, where M is a metal ion such as sodium, potassium or calcium, or ammonium.

A typical cationic group is preferably a quaternary alkylammonium group, and a counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like.

Preferred examples of the compound represented by formula (2) which can be used in the present invention are shown below, but the present invention is not limited thereto.

The following compounds are mentioned as examples of the betaine type.
I can do it. (2) -1. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourCOO^- (2) -2. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- (2) -3. (CF_ThreeO) (PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourSO_Three-(2) -4. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_ThreeH₆SO_Three ^- (2) -5. (CF_ThreeO) (PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_ThreeH₆SO_Three ^- (2) -6. [(CF_ThreeO)_Three(PFC) -COOC
H_Two]_TwoCH-CONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three
^- (2) -7. [(CF_ThreeO)_Two(PFC) -COOC
H_Two]_TwoCH-CONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three
^- (2) -8. [(CF_ThreeO) (PFC) -COOCH_Two]
_TwoCH-CONHC_ThreeH ₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- Examples of the cationic type include the following.

(2) -9. (CF_ThreeO)_Three(PFC) -C
ONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourOH ・ Cl^- (2) -10. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoC_TwoH _FourOH ・ Cl^- (2) -11. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆N⁺(CH_Three)_TwoC_TwoH_FourOH ・ Cl^- (2) -12. (CF_ThreeO)_Three(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoH ・ Cl^- (2) -13. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoH ・ Cl^- (2) -14. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆N⁺(CH_Three)_TwoH ・ Cl^- (2) -15. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- (2) -16. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- (2) -17. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- (2) -18. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- (2) -19. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- (2) -20. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- Examples of the nonionic type include the following compounds.

(2) -21. _{(CF 3 O) 3 (PFC} ) -
_{COO (C 2 H 4 O)} 12 H (2) -22. _{(CF 3 O) 2 (PFC} ) -COO (C 2
_{H 4 O) 12 H (2} ) -23. _{(CF 3 O) (PFC)} -COO (C 2 H
₄ O) ₁₂ H (2) -24. _{(CF 3 O) 3 (PFC} ) -COO (C 2
_{H 4 O) 15 CH 3 (} 2) -25. _{(CF 3 O) 2 (PFC} ) -COO (C 2
_{H 4 O) 15 CH 3 (} 2) -26. _{(CF 3 O) (PFC)} -COO (C 2 H
₄ O) ₁₅ CH ₃ (2) -27. [(CF ₃ O) ₃ (PFC) -COOCH
₂ ] ₂ CHC ₃ H ₆ OH (2) -28. [(CF ₃ O) ₂ (PFC) -COOCH
₂ ] ₂ CHC ₃ H ₆ OH (2) -29. _{[(CF 3 O) (PFC)} -COOC
Examples of the anion type [H ₂ ] ₂ CHC ₃ H ₆ OH include the following compounds.

(2) -30. (CF_ThreeO)_Three(PFC)-
CONHC_ThreeH₆COONa (2) -31. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆COONa (2) -32. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆COOK (2) -33. (CF_ThreeO)_Three(PFC) -CONHC_Three
H₆SO_ThreeNa (2) -34. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆SO_ThreeNa (2) -35. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆SO_ThreeK (2) -36. (CF_ThreeO)_Three(PFC) -CON (C_Three
H₆SO_ThreeNa) C_ThreeH₇ (2) -37. (CF_ThreeO)_Two(PFC) -CON (C_Three
H₆SO_ThreeNa) C_ThreeH₇ (2) -38. (CF_ThreeO) (PFC) -CON (C_ThreeH
₆SO_ThreeNa) C_ThreeH₇ (2) -39. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) COONa (2) -40. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) COONa (2) -41. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) COONa (2) -42. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (COONa) _Two (2) -43. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (COONa) _Two (2) -44. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (COONa)_Two (2) -45. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) SO_ThreeNa (2) -46. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) SO_ThreeNa (2) -47. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) SO_ThreeNa (2) -48. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆SO_ThreeNa (2) -49. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆SO_ThreeNa (2) -50. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoCHC_ThreeH₆SO_ThreeHowever, in the above, (PFC) is a perfluorocyclo
Represents an alkylene group; (CF_ThreeThe substitution position of O) is
With the carbonyl group as the 1-position, (CF_ThreeO)_ThreeIn the case of 3, 4,
5th place, (CF_ThreeO)_TwoIs third and fourth place,
(CF_ThreeIn the case of O), it is the fourth place.

The method for synthesizing the above-mentioned fluorine-based surfactant is described in JP-A-10-158218, JP-T-2000-5.
No. 05803 can be referred to.

The compound represented by the general formula (3) is described
I will tell. In the general formula (3), Rf is at least
L represents an alkyl group containing one fluorine atom;₁You
And L_TwoEach represents a mere bond or a linking group;
Is hydrogen atom, hydroxy group, anionic group, cationic
A group or an amphoteric group; ₁And R_TwoIs a hydrogen atom
Or a lower alkyl group. m and n are each a polymerization
Represents a molar ratio, m + n = 1.0, and p is an integer of 1 or more.
Represents a number.

Rf represents an alkyl group containing at least one fluorine atom, and preferably has 3 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and preferably 4 to 10 carbon atoms.
It is particularly preferable that the number is from 7 to 7.

L ₁ and L ₂ each represent a mere bond or a linking group, and the linking group represents a hetero atom, a carbonyl group, an amide group, or an alkylene group (for example, an oxyalkylene group) bonded thereto. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.

X represents a hydrogen atom, a hydroxy group, an anionic group, a cationic group or an amphoteric group, and the anionic group is preferably a carboxy group, a sulfonic acid group, or a phosphate group.
Alkali metal ions such as potassium ions and ammonium ions are preferred. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like.

The amphoteric group is preferably a group in which the above-mentioned cationic group and anionic group are bonded.

R ₁ and R ₂ each represent a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, etc.). m
And n each represent a polymerization molar ratio and m + n = 1.0, preferably 0.3 ≦ m ≦ 0.9, 0.1 ≦ n ≦
0.7.

In the present invention, different monomers having an Rf group may be copolymerized, or different monomers having an X group may be copolymerized. That is, m = m1 + m2 + m3 +..., N = n1 + n2 +
.. may be of a composite type.

P represents an integer of 1 or more, an anionic group,
A plurality of cationic groups, nonionic groups and amphoteric groups may be present. Preferably, p is an integer of 1 or more and 5 or less.

The weight average molecular weight of the high molecular weight fluorine-containing compound of the present invention is 500,000 or less, preferably 5,000 to 300,000. When the molecular weight is larger than the above, the viscosity of the coating solution for the photographic constituent layer is increased and the wet strength of the coating film is decreased, which is not preferable.

Preferred specific examples of the compound represented by formula (3) which can be used in the present invention are shown below, but the present invention is not limited thereto.

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[0051]

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[0052]

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[0054]

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The method for synthesizing the fluorine-based surfactant is described in JP-A-10-501591 and JP-A-11-5043.
No. 60 and JP-A-2000-263714 can be referred to. High contrast agent One of the features of the present invention is that a high contrast agent is contained on the side having silver halide. The high contrast agent is not particularly limited, but preferably contains at least one selected from substituted alkene derivatives, substituted isoxazole derivatives, specific acetal compounds and hydrazine derivatives.

Among the substituted alkene derivatives, substituted isoxazole derivatives and specific acetal compounds, the compounds represented by the above formula (N-1), (N-2) or (N-3), that is, the compounds represented by the formula (N Preferred are a substituted alkene derivative represented by -1), a substituted isoxazole derivative represented by general formula (N-2), and a specific acetal compound represented by general formula (N-3).

The substituted alkene derivative represented by the general formula (N-1) will be described. In the general formula (N-1), R
¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (N-1), R ¹ and Z, R ² and R ³ , R ¹ and R ² ,
Alternatively, R ³ and Z may combine with each other to form a cyclic structure.

When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom) and an alkyl group (an aralkyl group, a cycloalkyl group). Groups, active methine groups, etc.), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (including N-substituted nitrogen-containing heterocyclic groups), and heterocyclic groups containing quaternized nitrogen atoms (eg, Pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, imino group, imino group substituted by N atom, thiocarbonyl group, sulfonylcarbamoyl group, acylcarbamoyl group, sulfa Moylcarbamoyl, carbazoyl, oxalyl, oxamoyl, cyano, thiocarbamoyl, Loxy group or a salt thereof, alkoxy group (including a group repeatedly containing ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group , A sulfonyloxy group, an amino group, an (alkyl, aryl or heterocycle) amino group, an acylamino group, a sulfonamide group, a ureido group, a thioureido group,
Imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido Group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocycle) thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group,
Examples include a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphoryl group, a group having a phosphoric acid amide or a phosphoric ester structure, a silyl group, and a stannyl group. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the general formula (N-1) is a substituent whose Hammett's substituent constant σp can take a positive value. Specifically, a cyano group ,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom, perfluoroalkyl group, A fluoroalkaneamide group, a sulfonamide group, an acyl group, a formyl group, a phosphoryl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), a heterocyclic group, an alkenyl group,
Examples include an alkynyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, and an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is a saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group, a pyrazinyl group, a quinoxalinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, a hydantoin-1-yl group , A succinimide group, a phthalimide group and the like.

The electron-withdrawing group represented by Z in the general formula (N-1) may further have a substituent, and examples of the substituent include R ¹ in the general formula (N-1), The same substituents as R ² and R ³ may have when they represent a substituent are exemplified.

In the general formula (N-1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. The cyclic structure formed at this time is a non-aromatic carbon ring or a non-aromatic hetero ring.

Next, the preferred range of the compound represented by formula (N-1) will be described. The silyl group represented by Z in the general formula (N-1) is preferably a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a trimethylsilyldimethylsilyl group. And so on.

The electron-withdrawing group represented by Z in the formula (N-1) is preferably a group having a total carbon number of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group. Group, thiocarbonyl group, imino group, imino group substituted by N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group,
A formyl group, a phosphoryl group, an acyloxy group, an acylthio group, or a phenyl group substituted with an arbitrary electron-withdrawing group, and more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group, or an alkyl group. A sulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group, and particularly preferably a cyano group, a formyl group, an acyl group, It is an alkoxycarbonyl group, an imino group or a carbamoyl group. In the general formula (N-1), Z
The group represented by is more preferably an electron-withdrawing group.

In the general formula (N-1), R ¹ , R ² , R ³
Preferably, the substituent represented by
Specifically, a group having the same meaning as the electron-withdrawing group represented by Z in the above general formula (N-1), and an alkyl group, a hydroxy group (or a salt thereof), and a mercapto group (or a salt thereof) ), An alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group,
Examples include a heterocyclic amino group, a ureido group, an acylamino group, a sulfonamide group, and a substituted or unsubstituted aryl group.

Further, in the general formula (N-1), R ¹ is
Preferred are an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom, and a silyl group.

When R ¹ represents an electron-withdrawing group, preferably the following groups having a total of 0 to 30 carbon atoms, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), Or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, a carboxy group (or a salt thereof) Or a saturated or unsaturated heterocyclic group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a saturated or unsaturated heterocyclic group.

When R ¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms in total, and examples of the substituent include arbitrary substituents.
Among them, an electron-withdrawing substituent is preferable.

In formula (N-1), R ¹ is more preferably an electron-withdrawing group or an aryl group.

In the general formula (N-1), the substituents represented by R ² and R ³ are preferably, specifically, an electron-withdrawing group represented by Z in the general formula (N-1). Synonymous group, alkyl group, hydroxy group (or salt thereof), mercapto group (or salt thereof), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkyl Amino group, anilino group, heterocyclic amino group, acylamino group,
And a substituted or unsubstituted phenyl group.

In the general formula (N-1), R ² and R
³ is more preferably one of them is a hydrogen atom,
This is when the other represents a substituent. The substituent is preferably an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group. Group, alkylamino group, anilino group, heterocyclic amino group, acylamino group (particularly perfluoroalkaneamide group), sulfonamide group, substituted or unsubstituted phenyl group, heterocyclic group, etc., and more preferably hydroxy group (Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group, and particularly preferably a hydroxy group (or A salt thereof), an alkoxy group or a heterocyclic group.

In the general formula (N-1), it is also preferable that Z and R ¹ , or R ² and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbon ring or a non-aromatic hetero ring,
It is a ring structure having 7 to 7 members, and its total carbon number including a substituent is preferably 1 to 40, more preferably 3 to 30.

Among the compounds represented by formula (N-1), one of the more preferable ones is that Z is a cyano group, formyl group, acyl group, alkoxycarbonyl group, imino group,
Or a carbamoyl group, R ¹ represents an electron-withdrawing group or an aryl group, one of R ^{2 and} R ³ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof) or a mercapto group (or a salt thereof) , An alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group. Furthermore, one of the particularly preferable compounds represented by the general formula (N-1) is that Z and R ^{1 form a} non-aromatic 5- to 7-membered cyclic structure, and R ² Or one of R ³ is a hydrogen atom, the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof),
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
It is a compound representing an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group. At this time, Z which forms a non-aromatic cyclic structure together with R ¹ is an acyl group,
A carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group and the like are preferable, and R ¹ is an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom. , An acylamino group, a carbonylthio group and the like.

Next, the substituted isoxazole derivative represented by the general formula (N-2) will be described.

In the general formula (N-2), R ⁴ represents a substituent. As the substituent represented by R ⁴ , a compound represented by the general formula (N-
The same substituents as those described for the substituents of R ¹ , R ² and R ^{3 in} 1) can be mentioned.

The substituent represented by R ⁴ is preferably an electron-withdrawing group or an aryl group. When R ⁴ represents an electron-withdrawing group, preferably the following groups having a total carbon number of 0 to 30,
That is, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group,
A phosphoryl group, an imino group, or a saturated or unsaturated heterocyclic group, a cyano group, an acyl group, a formyl group,
Alkoxycarbonyl, carbamoyl, sulfamoyl, alkylsulfonyl, arylsulfonyl, and heterocyclic groups are more preferred. Particularly preferably, a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group,
It is a carbamoyl group or a heterocyclic group.

When R ⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and examples of the substituent include R ¹ and R ² of the general formula (N-1). ,
When R ³ represents a substituent, the same as those described as the substituent can be mentioned.

R ⁴ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group or a substituted or unsubstituted phenyl group, and most preferably a cyano group, a heterocyclic group or an alkoxycarbonyl group. is there.

Next, the specific acetal compound represented by formula (N-3) will be described in detail.

In the general formula (N-3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group. , Anilino group, heterocyclic thio group, heterocyclic oxy group or heterocyclic amino group. X and Y or A and B may be bonded to each other to form a cyclic structure.

The substituents represented by X and Y in the general formula (N-3) include R ¹ , R ² and R ^{3 in the} general formula (N-1).
And the same substituents as described above. Specifically, alkyl groups (including perfluoroalkyl groups, trichloromethyl groups, etc.), aryl groups, heterocyclic groups, halogen atoms, cyano groups, nitro groups, alkenyl groups, alkynyl groups, acyl groups, formyl groups, alkoxy groups Carbonyl group, aryloxycarbonyl group, imino group, imino group substituted with an N atom, carbamoyl group, thiocarbonyl group, acyloxy group, acylthio group, acylamino group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphoryl group, carboxy Group (or its salt), sulfo group (or its salt), hydroxy group (or its salt), mercapto group (or its salt), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero group Ring thio group, amino group, alkylami Group, anilino group, heterocyclic amino group, a silyl group, and the like.

These groups may further have a substituent. X and Y may be bonded to each other to form a cyclic structure, and the cyclic structure formed in this case may be a non-aromatic carbon ring or a non-aromatic hetero ring. .

The substituents represented by X and Y in the general formula (N-3) are preferably groups having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and include a cyano group and an alkoxy group. Carbonyl group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted by N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group , A phosphoryl group, an acylamino group, an acyloxy group, an acylthio group, a heterocyclic group, an alkylthio group, an alkoxy group or an aryl group.

In the general formula (N-3), X and Y are more preferably a cyano group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a formyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a sulfamoyl group. , An alkylsulfonyl group, an arylsulfonyl group, an imino group, an imino group substituted with an N atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, a substituted phenyl group, and the like. Particularly preferred are a cyano group and an alkoxycarbonyl group. Group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylthio group, acylamino group, thiocarbonyl group, formyl group, imino group, imino group substituted with N atom, heterocyclic group, or any electron-withdrawing property And a phenyl group substituted with a group.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the formed cyclic structure is preferably a 5- to 7-membered ring, and has a total carbon number of 1 to 40, and more preferably 3 to 7 members.
30 is preferred. X and Y forming a cyclic structure include an acyl group, a carbamoyl group, an oxycarbonyl group,
Preferred are a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like.

In the general formula (N-3), A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic thio group, a heterocyclic oxy group or a heterocyclic oxy group. Represents a cyclic amino group, which may be bonded to each other to form a cyclic structure. The group represented by A or B in the general formula (N-3) is preferably a group having a total carbon number of 1 to 40, more preferably a group having a total carbon number of 1 to 30, and further has a substituent. Is also good.

In the general formula (N-3), A and B are
Are more likely to combine with each other to form a cyclic structure.
preferable. The ring structure formed at this time is a 5- to 7-membered ring.
Non-aromatic heterocycles are preferred and their total carbon number is from 1 to 4
0, more preferably 3 to 30. In this case, A, B
Are linked, for example, -O-
(CH_Two)_Two-O-, -O- (CH_Two)_Three-O-, -S-
(CH_Two)_Two-S-, -S- (CH_Two)_Three-S-, -Sp
h-S-, -N (CH_Three)-(CH_Two)_Two-O-, -N
(CH_Three)-(CH_Two)_Two-S-, -O- (CH_Two)_Two-S
-, -O- (CH_Two) _Three-S-, -N (CH_Three) -Ph-
O-, -N (CH_Three) -Ph-S-, -N (ph)-
(CH_Two)_Two-S- and so on.

The substituted alkene derivative represented by the general formula (N-1), the substituted isoxazole derivative represented by the general formula (N-2) and the specific compound represented by the general formula (N-3) according to the present invention. Acetal compound (hereinafter, represented by general formula (N-1)
To the compound represented by the general formula (N-3)) may incorporate a adsorptive group that adsorbs to silver halide. Examples of such an adsorptive group include U.S. Pat.
385,108 and 4,459,347, JP-A-5
Nos. 9-195233, 59-200231 and 59
No.-201045, No.59-201046, No.59-
No. 201047, No. 59-201048, No. 59-2
01049, JP-A-61-170733, and 61-170733.
Nos. 270744, 62-948, 63-2342
No. 44, No. 63-234245, No. 63-23424
The groups described in No. 6 are exemplified. These adsorbing groups to silver halide may be precursors.
As such a precursor, JP-A-2-28534
The groups described in No. 4 are exemplified.

The compounds represented by the general formulas (N-1) to (N-3) according to the present invention contain a ballast group or a polymer commonly used in immobile photographic additives such as couplers. May be incorporated. Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group,
It can be selected from an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

The compounds represented by the general formulas (N-1) to (N-3) according to the present invention contain a cationic group (specifically, a group containing a quaternary ammonium group, Or 4
Nitrogen-containing heterocyclic group containing a graded nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl or heterocyclic) thio group, or a dissociable group dissociable by a base (A carboxy group, a sulfo group, an acylsulfamoyl group, a carbamoylsulfamoyl group, etc.). Particularly, those containing a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group or a (alkyl, aryl or heterocyclic) thio group are one of preferred examples of the present invention. Specific examples of these groups include, for example, JP-A-7-234471 and JP-A-5-33346.
6, JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat.
No. 65, U.S. Pat. No. 4,988,604, JP-A-3-2
59240, JP-A-7-5610, JP-A-7-24
No. 4348, German Patent No. 4006032 and the like.

Next, specific examples of the compounds represented by formulas (N-1) to (N-3) according to the present invention are shown below.
However, the present invention is not limited to the following compounds.

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The compounds represented by the general formulas (N-1) to (N-3) according to the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol) And ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve. An emulsified dispersion can be prepared and used. Alternatively, the compound powder can be dispersed and used in a suitable solvent such as water by a ball mill, a colloid mill or ultrasonic waves by a method known as a solid dispersion method.

The compounds represented by the general formulas (N-1) to (N-3) according to the present invention can be used as a layer on the image forming layer side with respect to the support, that is, on the image forming layer or on the layer side. It may be added to any other layer, but is preferably added to the image forming layer or a layer adjacent thereto.

The addition amount of the compounds represented by formulas (N-1) to (N-3) according to the present invention is preferably 1 × 10 ^-6 to 1 mol per 1 mol of silver, and more preferably 1 × 10 ^-6 to 1 mol. 10 ^{-5 to} 5 × 1
0 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is particularly preferred.

The compounds represented by formulas (N-1) to (N-3) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515 and US Pat. No. 5,635,339, U.S. Pat.
No. 30, International Patent WO-97 / 34196,
The compound can be synthesized with reference to the methods described in 1-1133546 and JP-A-11-95365.

The compounds represented by the general formulas (N-1) to (N-3) according to the present invention can be obtained by using only one compound.
More than one species may be used in combination. In addition to the above, US Pat. No. 5,545,515 and US Pat.
No. 9, U.S. Pat. No. 5,654,130, International Patent WO-
97/34196, U.S. Patent No. 5,686,228,
JP-A-11-119372, JP-A-11-13354
6, JP-A-11-119373, JP-A-11-10
9546, JP-A-11-95365, JP-A-11-95
Compounds described in JP-A-95366 and JP-A-11-149136 may be used in combination.

The hydrazine derivative will be described. In the present invention, a hydrazine derivative may be used as a high contrast agent, or the above-mentioned high contrast agent and a hydrazine derivative may be used in combination. In that case, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following patents.

(Chemical 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, from pages 8 to 1 of the publication
Compounds 1 to 38 described on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H described on pages 8 to 15 of the same publication
-1 to H-44. As described in Japanese Patent Application No. 7-191007,
A compound characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, particularly a compound represented by the general formula (A), the general formula (B) or the general formula ( C), compounds represented by formulas (D), (E) and (F), specifically, compounds N-1 to N-30 described in the same publication. Japanese Patent Application 7-1
Compounds represented by the general formula (1) described in JP-A-91007, specifically, compounds D-1 to D-5 described in the same publication
5.

Further, various hydrazine derivatives described on pages 25 to 34 of “Known Techniques (pages 1 to 207)” (published on March 22, 1991) (Aztec). JP 62
Compounds D-2 and D of -86354 (pages 6 to 7)
-39.

The hydrazine derivative used in the present invention is
It can be used by dissolving in a suitable organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve, and the like.

Further, by using a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve mechanically. An emulsified dispersion can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative used in the present invention is
The layer may be added to the image forming layer side of the support, that is, to the image forming layer or any other binder layer on the layer side, but it may be added to the image forming layer or a binder layer adjacent thereto. preferable.

The addition amount of the hydrazine derivative used in the present invention is preferably 1 × 10 ^-6 to 1 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-1 mol, and more preferably 2 × 10 ^-5 mol to 1 mol of silver.
Most preferably, it is 10 ^{-5 to} 2 × 10 ^-1 mol.

Further, the present invention provides a method for forming a super-high contrast image.
A high contrast accelerator can be used in combination with the above-mentioned high contrast agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5, and hydroxamic acids described in 5,545,507, specifically HA-1 to AM-5 Acrylonitrile described in HA-11, 5,545,507, specifically CN-1 to C
Hydrazine compounds described in N-13 and 5,558,983, specifically, CA-1 to CA-6, Japanese Patent Application No. 8-1.
Onium salts described in No. 32836, specifically A-
1 to A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

The synthesis method, addition method, addition amount and the like of these high contrast enhancement agents can be carried out as described in each of the cited patents.

The photothermographic material of the present invention will be described below. The photothermographic material of the invention contains an organic silver salt, silver halide and a reducing agent on one side of the support in a single layer or in a plurality of image forming layers in a dispersed state. Organic Silver Salt In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a heteroorganic acid containing a reducible silver ion source, particularly a long chain (10 to 30, preferably 15 to 30, 25
And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Disc
Closure (hereinafter simply referred to as RD) No. 17029
And 299963, and include: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver ( For example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc .; aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, formaldehyde, acetaldehyde, butyraldehyde, etc.). Silver complexes of polymeric reaction products of various aldehydes with hydroxy-substituted acids such as salicylic acid, benzylic acid 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid; silver salts or complexes of thiones (e.g., 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione and - carboxymethyl-4-methyl-4-thiazoline-2-thione); imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver and a nitrogen acid selected from 2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate and / or silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a controlled double jet method to produce organic silver salt crystals. At that time, silver halide grains may be mixed. Silver halide The silver halide in the present invention functions as an optical sensor. In the present invention, in order to suppress white turbidity after image formation, and to obtain good image quality, it is preferable that the average particle size is small, the average particle size is 0.1 μm or less,
More preferably 0.01 to 0.1 μm, especially 0.02 to
0.08 μm is preferred. Here, the grain size refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. or,
In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. The silver halide grains are preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The degree of monodispersion is preferably 30% or less, particularly preferably 0.1 to 20%.
%.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the silver halide particles have an average particle size of 0.1.
μm or less, and more preferably monodisperse particles,
Within this range, the granularity of the image is improved.

The shape of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, and more preferably 7% or more.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by T.M. using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide grains is tabular grains. Here, the tabular grains are:
When the square root of the projected area is r μm and the vertical thickness is h μm, the aspect ratio = r / h is 3 or more. Among them, the aspect ratio is preferably 3
~ 50. The particle size is preferably 0.1 μm or less, and more preferably 0.01 to 0.08 μm. These are disclosed in U.S. Patent Nos. 5,264,337 and 5,314,134.
No. 798, 5,320,958, etc., and the desired tabular grains can be easily obtained. When these tabular grains are used in the invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements for the purpose of improving illuminance failure and adjusting the improvement. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

The silver halide grains can be desalted by washing with a method known in the art such as a noodle method or a flocculation method, but in the present invention, they may or may not be desalted. .

The silver halide in the present invention is preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, and noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, as well known in the art. A sensitization method can be appropriately selected and used.

In the present invention, in order to prevent devitrification of the photothermographic material, the total amount of silver halide grains and organic silver salts is 0.3 to 2.2 g per m ² in terms of silver. , 0.5 g to 1.5 g is more preferable. With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is 50% or less by mass, preferably 2%.
5% or less, more preferably 0.1 to 15%.

The spectral sensitizing dye to be used in the present invention may be optionally used, for example, as described in JP-A-63-159814 and JP-A-60-15941.
140335, 63-231437, 63-2
No. 59651, No. 63-304242, No. 63-15
No. 245, U.S. Pat. Nos. 4,639,414,
The sensitizing dyes described in 740,455, 4,741,966, 4,751,175, 4,835,096 and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RDItem
Section 17643 IV-A (p. 23, December 1978),
Item 1831X (August 1978, p. 437)
Or cited in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected, for example, as described in JP-A-9-34078, JP-A-9-54409, and JP-A-9-80679. Sensitizing dyes are preferably used. Reducing Agent The photothermographic material of the invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Pat.
0,448, 3,773,512, 3,59
No. 3,863, and RD Nos. 17029 and 29963.

Aminohydroxycycloalkenones (eg, 2-hydroxy-3-piperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents N-hydroxyurea derivatives (e.g., Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (e.g., anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; Hydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenes Sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone Tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydroquinoxaline); amide oximes; azines; combinations of aliphatic carboxylic acid arylhydrazides and ascorbic acid; combinations of polyhydroxybenzene and hydroxylamine; Reductone and / or hydrazine; Hydroxanoic acids; Combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives;
A combination of -naphthol and a 1,3-dihydroxybenzene derivative; 5-pyrazolone; a sulfonamide phenol reducing agent; 2-phenylindane-1,3-dione and the like; chroman; 1,4-dihydropyridines (for example,
2,6-dimethoxy-3,5-dicarbethoxy-1,
4-dihydropyridine); bisphenols (for example,
Bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane , 4,4-ethylidene-bis (2-t-butyl-6-methylphenol)), ultraviolet-sensitive ascorbic acid derivatives; hindered phenols; 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Oxidizing agent The photothermographic material of the invention preferably contains an oxidizing agent. The oxidizing agent used in the present invention may be any oxidizing agent as long as it reduces fog during storage.
Such oxidizing agents are preferably, for example, those described in JP-A-50-119624, JP-A-50-120328, JP-A-51-121332, JP-A-54-58022, and JP-A-56-58022.
-70543, 56-99335, 59-90
No. 842, No. 61-129,642, No. 62-1298
No. 45, JP-A-6-208191, and JP-A-7-5621
Nos. 7-2781, 8-15809, U.S. Pat. Nos. 5,340,712 and 5,369,000,
Nos. 5,464,737 and 3,874,946
No. 4,756,999 and 5,340,71
No. 2, EP 605981 A1, EP 622666
A1 and 631176A1, JP-B 54-165
Nos. 4,180,665 and 4,44.
Compounds described in No. 2,202 can be used, but polyhalogen compounds are preferred.

In the present invention, the amount of the oxidizing agent is preferably 1 × 10 ^-4 to 1 mol per mol of silver, and more preferably 1 × 10 ^-4 to 1 mol.
More preferably, it is 10 ^{-3 to} 0.5 mol.

It is preferred that at least one layer on the image forming layer side of the photothermographic material of the present invention contains a fatty acid and a derivative thereof. Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, and the like. Examples of stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, elaidic acid, and fatty acid esters include, for example, butyl stearate, amyl stearate, octyl stearate, butyl palmitate, butyl myristate, and butoxyethyl stearate. Rate, oleyl oleate, butoxyethyl stearate.

The above-mentioned materials and the like may be contained in at least one layer on the image forming layer side of the photothermographic material of the present invention. Layers may be provided and added separately to each layer. Binder Suitable binders for the photothermographic material of the present invention are transparent or translucent, generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly ( Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), Copoly (styrene-
Maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters),
There are poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

Other preferred binders are the polymer latexes described below. The polymer latex is preferably contained in the image forming layer. The polymer latex preferably contains at least 50% by mass of the entire binder. In the present invention, the “polymer latex” is obtained by dispersing a water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used.

The polymer latex in the present invention is described in "Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kankai (1978))", "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Edited by Keiji Kasahara, published by the Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, published by the Society of Polymer Publishing (197)
0))).

The average particle size of the dispersed particles is 1 to 50,000 n.
m, more preferably in the range of about 5 to 1,000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution. As the polymer latex, a so-called core / polymer latex other than an ordinary polymer latex having a uniform structure is used.
Shell type latex may be used. In this case, it may be preferable to change the glass transition temperature of the core and the shell. Minimum film formation temperature (MFT) of the polymer latex of the present invention
Is preferably -30 to 90C, more preferably about 0 to 70C. In order to control the minimum film forming temperature, a film forming auxiliary may be added. The film-forming aid is also called a plasticizer, and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex. For example, the above-mentioned “Synthetic latex chemistry (Souichi Muroi, published by Kobunshi Kankokai (197)
0)) ".

Examples of the polymer used for the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. Also, the polymer may be a so-called homopolymer in which a single monomer is polymerized,
A copolymer obtained by polymerizing two or more monomers may be used. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is 5,000 to 1,000,000, preferably 10,000, in number average molecular weight.
About 100 to 100,000 is preferable. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder for the image forming layer of the photothermographic material of the present invention include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic. Acid copolymer latex, styrene / butadiene / acrylic acid copolymer latex, styrene / butadiene / divinylbenzene / methacrylic acid copolymer latex, methyl methacrylate / vinyl chloride / acrylic acid copolymer latex, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid Latex of a copolymer and the like.

Further, such polymers are also commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635, 465
83, 4601 (all manufactured by Daicel Chemical Industries, Ltd.);
Nipol Lx811, 814, 821, 820, 8
Polyester resins such as 57 (both manufactured by Nippon Zeon Co., Ltd.) include FINETEX ES650, 611,
675, 850 (all manufactured by Dainippon Ink and Chemicals, Inc.),
Examples of polyurethane resins such as WD-size and WMS (all manufactured by Eastman Chemical) include HYDRAN.
Examples of rubber-based resins such as AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR.
7310K, 3307B, 4700H, 7132C
(Dai Nippon Ink Chemical Co., Ltd.), Nipol L
x416, 410, 438C, 2507, and the like (all manufactured by Nippon Zeon Co., Ltd.)
51, G576 (all manufactured by Nippon Zeon Co., Ltd.); vinylidene chloride resins such as L502 and L513 (all manufactured by Asahi Chemical Industry Co., Ltd.); olefin resins include Chemipearl S120 and SA100 (all manufactured by Mitsui Oil) Chemical Co., Ltd.). These polymers may be used alone or as a mixture of two or more as necessary.

The polymer latex preferably contains a carboxylic acid component such as an acrylate or methacrylate component in an amount of about 0.1 to 10% by mass. When a polymer latex is used for the image forming layer, the image forming layer is preferably such that at least 50% by mass of the total binder is the above polymer latex, and more preferably at least 70% by mass is the above polymer latex. In that case, if necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose is added to the image forming layer in a range of 50% by mass or less of the entire binder. Is also good. The addition amount of these hydrophilic polymers is preferably 30% by mass or less of the total binder in the image forming layer.

When a polymer latex is used for the image forming layer, the image forming layer is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 50% by mass or more of the solvent (dispersion medium) of the coating liquid is water, and preferably 65% by mass or more of the solvent is water. As components other than water of the coating liquid, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide =
80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent mass%.) A crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added to the image forming layer. When the image forming layer contains a polymer latex, the coating solution for the thermal image forming layer is preferably a so-called thixotropic fluid. The thixotropic property refers to a property in which the viscosity decreases as the shear rate increases. Although any apparatus may be used for the viscosity measurement, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used, and the viscosity is measured at 25 ° C. The organic silver salt-containing fluid or the thermal image forming layer coating solution in the invention has a shear rate of 0.1.
The viscosity in S-1 is 400 mPa · s or more, 100,
000 mPa · s or less, more preferably 5 mPa · s or less.
It is not less than 00 mPa · s and not more than 20,000 mPa · s. At a shear rate of 1000 S-1, 1 mP
It is preferably not less than a · s and not more than 200 mPa · s, and more preferably not less than 5 mPa · s and not more than 80 mPa · s.

Various systems exhibiting thixotropic properties are known, and are described in, for example, “Lecture / Rheology” edited by Polymer Publishing Association, “Polymer Latex”, co-authored by Muroi and Morino (published by Polymer Publishing Association). In order for the fluid to exhibit thixotropic properties, it is necessary to contain a large amount of solid fine particles. In order to enhance the thixotropic property, the thickening linear polymer is contained, the aspect ratio is increased by the anisotropic solid fine particles contained, alkali thickening,
Use of a surfactant is effective.

The total amount of the binder in the image forming layer is from 0.2 to 3
0 g / m ^2, more preferably in the range of 1 to 15 g / m ^2.

In order to protect the surface of the photothermographic material and prevent abrasion, a non-image forming layer may be provided outside the image forming layer. The binder used for these non-image forming layers may be the same or different from the binder used for the image forming layers.

In the present invention, the amount of binder in the photosensitive layer is preferably 0.5 to 30 g / m ² in order to increase the speed of thermal development. More preferably, 1 to 15 g / m
² If it is less than 0.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable. Supports As the support of the photothermographic material, paper, paper coated with polyethylene, paper coated with polypropylene, parchment,
A cloth, a sheet or thin film of metal (eg, aluminum, copper, magnesium, zinc), a glass plate, a glass plate coated with a metal (eg, chromium alloy, steel, silver, gold, platinum), a plastic film, or the like can be used. It is possible but preferably a plastic film. As the plastic of the plastic film used for the support, for example,
Polyalkyl methacrylate (eg, polymethyl methacrylate), polyester (eg, PET), polyvinyl acetal, polyamide (eg, nylon) and cellulose ester (eg, cellulose nitrate, cellulose acetate, cellulose, acetate propionate, cellulose acetate butyrate) Rate). The support may be coated with a polymer. Examples of the polymer include polyvinylidene chloride, an acrylic acid-based polymer (eg, polyacrylonitrile, methyl acrylate), a polymer of unsaturated dicarboxylic acid (eg, itaconic acid, acrylic acid), carboxymethylcellulose, and polyacrylamide. Copolymers may be used. Instead of coating with a polymer, an undercoat layer containing a polymer may be provided. In order to improve the dimensional characteristics of the support, the support is preferably subjected to an annealing treatment under low tension. For example,
0-22616, U.S. Pat. No. 2,779,684,
RD 19809, JP-A-8-211547, 10
No.-10676, No.10-10677, No.11-47
No. 676, No. 11-65025, No. 11-13862
No. 8, No. 11-138648, No. 11-221892
It is preferable to appropriately combine known methods described in JP-A Nos. 11-333922 and 11-333923. The tension during the heat treatment of the support, preferably during the application of the undercoat layer, is 0.4 to 80 N / cm ² , more preferably ^{2 to} 80 N / cm ² .
60N / cm ^2, more preferably from 10 to 50 N / cm ^2. The heat treatment temperature or drying temperature is 70 to 220 ° C, more preferably 80 to 200 ° C, and further preferably 9 to 220 ° C.
0-190 ° C. Heat treatment time or drying time is 1
The time is preferably from 30 to 30 minutes, more preferably from 2 to 20 minutes, and still more preferably from 3 to 15 minutes.

As a preferred example of the layer constitution in the present invention, an undercoat layer is provided on one surface of the support, an image recording layer is provided thereon, and a surface protective layer is further provided thereon. The undercoat layer (image forming layer side) may have two or more layers, and the total dry film thickness of the undercoat layer is preferably 0.2 to 5 μm, and 0.5 to 3 μm.
More preferably, it is μm. The dry film thickness of the image forming layer is preferably from 5 to 13 μm, more preferably from 7 to 11 μm. The dry thickness of the surface protective layer is 2
It is preferably 10 μm. The surface protective layer preferably contains a matting agent. The average particle size of the matting agent is 1 to
12 μm is preferable, and 2 to 10 μm is more preferable. As the matting agent, known fillers can be used, but it is preferable to use an inorganic powder such as silica.

An undercoat layer is provided on the surface of the support opposite to the image forming layer, and a back coat layer is provided thereon.
Further, it is preferable to provide a back coat surface protective layer thereon. The undercoat layer (backcoat layer side) may be two or more layers, and at least one undercoat layer is preferably an antistatic layer containing a conductive metal oxide and / or a conductive polymer. As the conductive metal oxide, Sb
The surface treatment of SnO ₂ is preferable, and the conductive polymer is preferably polyaniline. The total dry film thickness of the undercoat layer is 0.
It is preferably from 2 to 4 μm, more preferably from 0.5 to 2 μm. The dry film thickness of the back coat layer is 2 to 10 μm
And more preferably 4 to 8 μm. The back coat layer preferably contains an antihalation dye. The dry film thickness of the back coat surface protective layer is preferably 2 to 10 μm. The back coat surface protective layer preferably contains a matting agent.
As the matting agent, known fillers can be used, but it is preferable to use an inorganic powder such as silica. The average particle size of the matting agent is preferably in the range of 1 to 15 μm,
The range of μm is more preferred. By adopting the above-described layer configuration and film thickness configuration, the effects of the present invention can be more effectively exerted.

The photothermographic material of the present invention is exposed using an infrared semiconductor laser having a wavelength of 700 to 100.
It is preferably 0 nm. In thermal development after exposure, 4
The ultra-rapid processing for 5 seconds or less is performed, and the heat development time is preferably "top to top" of 5 to 40 seconds or less, more preferably 5 to 30 seconds. Here, "top to
The term "top" refers to the time from the moment when the leading end of the photothermographic material to be processed enters the film insertion portion of the heat developing machine to the moment when the processed front end of the photothermographic material comes out of the heat developing machine. In the present invention, the transfer speed of the heat developing machine is 2
It is preferably 2 to 40 mm / sec. 22mm
If it is less than / sec, a failure that increases fog may occur. If the speed exceeds 40 mm / sec, a failure such as a scratch on the surface may occur, or a transport failure may occur.

In the heat development process according to the present invention, 11
After passing through a preheating section at 0 ° C. for 15 seconds, it is preferable to carry out horizontal transfer in an oven and perform thermal development at 120 ° C. for 15 seconds.

The surface of the photothermographic material according to the present invention on the side having silver halide (image forming layer side) is brought into contact with a roller to drive the roller, and the side having silver halide relative to the support ( The means for carrying out thermal development processing by sliding the surface opposite to the image forming layer side (in the image forming layer side) into contact with a smooth surface and transporting it is described.

The photothermographic material of the present invention is usually developed by elevating the temperature of the photothermographic material exposed imagewise. The preferred development temperature is from 80 to 250C, more preferably from 100 to 140C. The development time is 1
The time is preferably from 180 to 180 seconds, more preferably from 10 to 90 seconds.

As a method for preventing processing unevenness due to dimensional change during thermal development of the photothermographic material of the present invention, after heating at a temperature of 80 ° C. or more and less than 115 ° C. (preferably 113 ° C. or less) for 5 seconds or more, A method of forming an image by thermal development at a temperature of at least 130 ° C. (preferably at most 130 ° C.) (a so-called multi-stage heating method) is effective.

In order to attain the object of the present invention, as a heat development processing device (heat development machine), the side having the image forming layer of the photothermographic material is driven while being in contact with a roller. It is preferable to use a device having a function of transporting the opposite back surface by sliding it on a smooth surface.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine 1 of FIG. 1 corrects the photothermographic material 2 into a planar shape and preheats the photothermographic material 2 while carrying in the heating section. The lower roller is a heat roller. It has a carry-out roller pair 4 for carrying out of the heating unit while correcting it into a planar shape. The photothermographic material 2 is thermally developed while being transported from the carry-in roller pair 3 to the carry-out roller pair 4. The conveying means for conveying the photothermographic material 2 during the heat development is provided with a plurality of rollers 5 on the side where the surface having the image forming layer contacts, and the non-woven fabric or the like on the side where the opposite back surface contacts. The bonded smooth surface 6 is provided. The back surface of the photothermographic material 2 is conveyed by sliding on the smooth surface 6 by driving a plurality of rollers 5 which come into contact with the surface having the image forming layer. As the heating means, a heater 7 is provided above the roller 5 and below the smooth surface 6 so as to heat the photothermographic material 2 from both sides. As a heating means in this case, a plate heater or the like can be used. Roller 5 and smooth surface 6
Is different depending on the member having a smooth surface, but is appropriately adjusted so that the photothermographic material 2 can be conveyed. Preferably it is 0 to 1 mm.

The material of the surface of the roller 5 and the member of the smooth surface 6 may be any material as long as it has high temperature durability and does not hinder the conveyance of the photothermographic material 2. The member is preferably a nonwoven fabric made of polyphenylene sulfide (PPS) or Teflon (R) (PTFE). It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section includes a preliminary heating section X having a carry-in roller pair 3 and a thermal development processing section Y having a heating heater 7.
The preheating section X upstream of the heat development processing section Y is lower than the heat development temperature (for example, about 10 to 20 ° C. lower), and is lower than the glass transition temperature of the support of the photothermographic material 2. It is preferable that the temperature is set so as not to cause uneven development at a high temperature. A guide plate 8 is provided downstream of the thermal development processing section Y.
Is installed, and a slow cooling section Z having a carry-out roller pair 4 and a guide plate 8 is installed. The guide plate is preferably made of a material having low thermal conductivity, and is preferably cooled gradually.

[0149]

EXAMPLES The present invention will be specifically described below with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 1. Preparation of Subbed PET Support 1 Plasma treatment 1 is performed on both sides of a biaxially stretched and heat-fixed PET film having a thickness of 125 μm under the following conditions, and then the subbing coating solution a-1 is dried on one side. After being applied so as to have a film thickness of 0.8 μm and dried, an undercoat layer A-1 was obtained.
On the other side, an undercoating coating solution b-1 having been subjected to the following antistatic treatment:
Was applied so as to have a dry film thickness of 0.8 μm and then dried to obtain an undercoat layer B-1 as a conductive layer. Next, the plasma treatment 2 was performed on the surface of each undercoat layer under the following conditions. << Plasma processing conditions >> Using a batch type atmospheric pressure plasma processing apparatus (AP-I-H-340, manufactured by EC Chemical Co., Ltd.), the high-frequency output was 4.5 kW, the frequency was 5 kHz,
Plasma treatment 1 and plasma treatment 2 were performed with a treatment time of 5 seconds and gas conditions of 90%, 5% and 5% by volume of argon, nitrogen and hydrogen, respectively. <Subbing coating liquid a-1> Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Styrene (25% by mass) 2-hydroxyethyl acrylate (25% by mass) copolymer latex liquid (solid content) 30%) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Colloidal silica (average particle size 90 μm) 0.1 g Finish to 1 liter with water Coating solution b-1> Tin oxide (average particle diameter of 36 nm doped with 0.1% of indium) An amount of 0.26 g / m ² Butyl acrylate (30% by mass) Styrene (20% by mass) Glycidyl acrylate (40% by mass) 270 g of a copolymer latex liquid (solid content: 30%) hexamethylene-1,6-bis (ethylene urea) In .8g water finish 1 liter with subbing drying <Support heat treatment> The resulting subbed support, the support is heated at 140 ° C., and then slowly cooled. It was conveyed at a tension of 1 × 10 ⁵ Pa at that time. 2. Coating on back layer surface side Back layer coating solution 1 and back protective layer coating solution 1 having the following compositions
Is filtered using a filter having an absolute filtration accuracy of 20 μm before each application, and then the total wet film thickness is 30 μm on the antistatic processed undercoat layer B-1 of the support prepared by the extrusion coater. As described above, simultaneous multi-layer coating was performed at a speed of 120 m / min, and drying was performed at 60 ° C. for 4 minutes. <Back layer coating solution 1> methylethylketone 16.4 g / m ² polyester resin (Bostic Co., Vitel PE2200B) 106mg / m ² infrared dye -C 37 mg / m ² stabilizer B-1 (from Sumitomo Chemical Co., Ltd. Sumilizer BPA) 20 mg / M ² stabilizer B-2 (Yoshitomi Pharmaceutical Tomisorb 77) 20 mg / m ² cellulose acetate propylate (Eastman Chemical Company CAP504-0.2) 1.0 g / m ² cellulose acetate butyrate (Eastman Chemical Company AB381-) 20) 1.0 g / m ²

[0151]

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<Coating Solution 1 for Back Protective Layer> Methyl ethyl ketone 22 g / m ² polyester resin (Bostic, Vitel PE2200B) 106 mg / m ² Antistatic agent; (CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₂ O -[CH ₃ SiO ｛CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₀ (CH ₂ CH ₂ CH ₂ O) ₁₅ CH ₃ }] ₃ O-Si (CH ₃ ) ₃ 22 mg / m ² fluorine Surfactant F-1: C ₈ F ₁₇ SO ₃ Li 10 mg / m ² Cellulose acetate propylate (Eastman Chemical Company CAP504-0.2) 1.0 g / m ² Cellulose acetate butyrate (Eastman Chemical Company AB381-20) ) 1.0 g / m ² matting agent (Fuji-Davison Co. Syloid 74; average particle size 7μm silica) 5 mg m ² 3. Preparation of Image Forming Layer (Preparation of Silver Halide Particles A) After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjusting the temperature to 40 ° C. and the pH to 5.0, silver nitrate 1
159 ml of an aqueous solution containing 8.6 g and an aqueous solution containing potassium bromide were added over 10 minutes by a controlled double jet method while keeping the pAg at 7.7. Then
476 ml of an aqueous solution containing 55.4 g of silver nitrate and K ₃ [Ir
Cl _{6] 3} ^- and an aqueous solution containing 1 mole / liter to 8 × 10 ^-6 mol / liter and potassium bromide, the pAg 7.7
, And added over 30 minutes by a controlled double jet method. Thereafter, the pH was adjusted to 5.9 and pAg to 8.0. The resulting grains were monodispersed cubic silver halide grains having an average particle size of 0.07 μm, a degree of dispersion of 15%, and a (100) face ratio of 85%. The silver halide grains were heated to a temperature of 60 ° C., and 8.5 × 10 ⁻⁵ mol of sodium thiosulfate and 1.1 × 10 ⁻⁵ mol of 2,3,
4,5,6-pentafluorophenyldiphenylphosphine selenide, 2 × 10 ⁻⁶ mol of tellurium compound-1,
3.3 × 10 ^-6 mol of chloroauric acid and 2.3 × 10 ^-4 mol of thiocyanic acid were added and the mixture was aged for 120 minutes. Thereafter, the temperature was raised to 50 ° C., 8 × 10 ^-4 mol of sensitizing dye C was added with stirring, and 3.5 × 10 ^-2 mol of potassium iodide was further added, followed by stirring for 30 minutes. The mixture was rapidly cooled to ℃ to complete the preparation of silver halide grains A.

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(Preparation of organic silver salt A microcrystal dispersion) 40 g of behenic acid, 7.3 g of stearic acid, 500 ml of distilled water
Was mixed at 90 ° C. for 15 minutes, 187 ml of a 1 mol / L aqueous NaOH solution was added over 15 minutes with vigorous stirring, and 61 ml of a 1 mol / L aqueous nitric acid solution was added at 50 ° C.
The temperature dropped. Next, a 1 mol / L silver nitrate aqueous solution 124 m
was added and the mixture was stirred for 30 minutes. Thereafter, the solid content was filtered by suction filtration, and the conductivity of the filtrate was 30 μS / c.
The solid content was washed with water until it reached m. The solid content thus obtained was treated as a wet cake without drying, and to a wet cake equivalent to 34.8 g of dry solid content, 12 g of polyvinyl alcohol and 150 ml of water were added.
Mix well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, disperse them in a dispersing machine (1 / 4G-sand grinder mill: manufactured by Imex Co., Ltd.) for 4 hours, and obtain a volume weighted average of 1 A monodispersed organic silver salt A microcrystal dispersion having a thickness of 2 μm and a degree of dispersion of 20% was obtained. The measurement of the particle size is performed by using the Master
SaizerX (Malvern Instrument
nts Ltd. Manufactured). To this dispersion was added a 6% methanol solution of phenylbromide perbromide for 3 m.
1 was added. When the silver halide in the dispersion was observed with an electron microscope, silver halide grains smaller than 0.01 μm could be observed. (Preparation of solid fine particle dispersion of each material) Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, phthalazine, Regarding tribromomethylsulfonylbenzene, each solid fine particle dispersion was prepared by the following method.

For 5.4 g of tetrachlorophthalic acid,
0.81 g of hydroxypropylcellulose and 94.2 of water
Then, the mixture was stirred well and left as a slurry for 10 hours. Then, 100 ml of zirconia beads having an average diameter of 0.5 mm and a slurry were put together in a vessel, and dispersed in a dispersing machine of the same type as that used for preparing the organic silver salt microcrystal dispersion for 5 hours to obtain a tetrahedral solution. A solid microcrystalline dispersion of chlorophthalic acid was obtained. As for the particle diameter of the solid fine particles of the solid microcrystal dispersion, 70% by mass was 1.0 μm or less. With respect to other materials, in order to obtain a desired average particle size, the amount of the dispersant used and the dispersion time were appropriately changed to obtain each solid fine particle dispersion. 4. Preparation of Each Coating Solution [Image Forming Layer Coating Solution A] The following components were added to the organic silver salt A microcrystal dispersion prepared above to prepare an image forming layer coating solution A.

Organic silver salt A microcrystal dispersion 1 mol Silver halide particles A 0.05 mol Binder: SBR latex (LACSTAR 3307B, manufactured by Dainippon Ink and Chemicals, Inc.) 430 g Tetrachlorophthalic acid 5 g 1,1-bis (2 -Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g Phthalazine 9.0 g Tribromomethylsulfonylbenzene 12 g 4-methylphthalic acid 7 g Hardening agent (described in Table 1) Amount shown in Table 1 Hydrazine derivative LACSTAR 3307B is a latex of a styrene-butadiene copolymer, the average particle size of the dispersed particles is 0.1 to 0.15 μm, and the polymer is 25 ° C., 60 ° C.
The equilibrium water content at% RH was 0.6%.

[0157]

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[Surface Protective Layer Coating Solution 1] 262 g of water was added to 500 g of 40% binder resin B, 14 g of benzyl alcohol and 2.5 g of compound D were used as a film-forming aid, and Cellsol 524 (manufactured by Chukyo Yushi Co., Ltd.) 5 g, 12 g of compound E, 1 g of compound F, 2 g of compound G, the amount of the compound of the general formula (1) or (2) shown in Table 1 and the amount of compound H
7.5 g of polymethyl methacrylate microparticles having an average particle size of 3 μm as a matting agent were sequentially added, and water was further added to 1000 g, and the viscosity at 25 ° C. was 5 cp.
A surface protective layer coating solution 1 having a pH of 4.5 was prepared.

[0159]

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Binder resin B: polyurethane having a cyclohexane ring having -SO ₃ Na (diphenylmethane diisocyanate / neopentyl glycol / ethylene glycol / cyclohexyl dimethanol / isophthalic acid / phthalic acid = 11/22/3/22/29/13)
(Mass ratio) as a raw material, Tg = 73 ° C.,
Trade name UR-8200 manufactured by Toyobo Co., Ltd.) 5. Preparation of Photothermographic Material Sample 101 The coating solution A for the image forming layer and the coating solution 1 for the surface protective layer prepared as described above were each filtered immediately before coating using a filter having an absolute filtration accuracy of 20 μm. Then, PET support 1
The image forming layer and the surface protective layer were sequentially discharged onto the surface of the undercoating layer A-1 from the slit of the extrusion die coater, and were laminated at the same time at a speed of 90 m / min to obtain a sample 101. Was. Eight seconds later, a drying temperature of 75
After drying for 5 minutes using hot air having a dew point of 10 ° C. and ambient temperature and humidity of 23 ° C., 50% RH, and a tension of 196 N / m (20 k
g / m). The coated silver amount of the image forming layer of the obtained sample was 1.5 g / m ² , and the surface protective layer was 2.5 μm in dry film thickness. 6. Exposure of Samples Each of the obtained samples was subjected to a longitudinal multi-mode using a high-frequency superposition method described in JP-A-59-130494.
With an exposure machine using a semiconductor laser of 0 nm as an exposure source,
Exposure through a wedge was performed from the image forming layer side. 7. Thermal Development Processing The exposed sample 101 was preheated at 105 ° C. for 20 seconds by a thermal developing machine having the configuration shown in FIG. 1 and subjected to a thermal development processing at 120 ° C. for 20 seconds. The transport speed of the heat developing machine in FIG. 1 was 28 mm / sec. [Evaluation of photographic performance in raw preservation] A sample obtained by coating and drying was divided into two, and one of them was subjected to humidity control in a dark room at 50 ° C. and 48% RH as a substitute evaluation of the raw preservation, and then was not allowed to pass moisture. After being stored in a bag in a sealed state for 3 days, the above exposure was performed and development was performed. The remaining two samples were stored in a dark room at 23 ° C. and 48% RH for 3 days, and then exposed and developed. Thereafter, both were evaluated for the following items. (Evaluation of fog in raw preservation) The UV transmission density of the unexposed portion of each of the heat-treated samples prepared was measured with an optical densitometer through a filter that cuts light of 420 nm or more. In the present invention, an X-Rite optical densitometer X-R is used.
UV fog, which is a value measured in Ultraviolet (ultraviolet) mode with item 361T, was regarded as fog. (Evaluation of gradation in raw preservation) The sensitometry of each heat-developed sample thus prepared was carried out, and the density of the characteristic curve was determined to be 0.
1. and concentration 2. Was determined as the slope of a straight line connecting. (Evaluation of Concentration in Raw Storage) Each heat-developed sample thus produced was subjected to sensitometry to measure the maximum concentration. (Evaluation of density unevenness (ie, development unevenness) in raw storage)
A sample that had been subjected to a substitute evaluation of raw preservability (50 ° C. for 3 days)
After the exposure, the transport speed of the heat developing machine is set to 30 mm /
The heat development was performed for sec. After the processing, density unevenness (namely, development unevenness) was visually evaluated. A sample having no density unevenness (that is, development unevenness) was ranked 5, and the rank was lowered to 4, 3, 2, and 1 as it occurred.
A rank lower than 3 is not practical.

Table 1 shows the above progress and results.

[0162]

[Table 1]

As is clear from Table 1, the sample of the present invention is superior to the comparative sample in all evaluation items.

Example 2 (Preparation of Subbed PET Support) Both sides of a biaxially stretched and heat-fixed 125 μm-thick PET film manufactured by Teijin Limited were subjected to the following plasma treatment 1, and then to one side. The following undercoating coating solution a-3 was applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-3. 3 is dry film thickness 0.8μ
m and dried to form an antistatic subbing layer B
-3. Next, the following plasma treatment 2 was applied to each undercoat layer surface.

<< Plasma Processing Conditions >> Batch type atmospheric pressure plasma processing apparatus (AP-IH manufactured by EC Chemical Co., Ltd.)
-340), the high frequency output was 4.5 kW, the frequency was 5 kHz, the processing time was 5 seconds, and the gas conditions were 90%, 5% and 5% by volume of argon, nitrogen and hydrogen, respectively. And plasma treatment 2 were performed.

<< Undercoat Coating Solution a-3 >> Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Styrene (25% by mass) 2-hydroxyethyl acrylate (25% by mass) copolymer latex solution (Solid content 30%) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Colloidal silica (average particle size 90 μm) 0.1 g Finish to 1 liter with water << Undercoating Coating Solution b-3 >> Tin oxide (average particle diameter 36 nm doped with 0.1% indium) An amount of 0.26 g / m ² Butyl acrylate (30% by mass), styrene (20% by mass), glycidyl Acrylate (40 mass%) copolymer latex liquid (solid content 30%) 270 g hexamethylene-1,6-bis ( In subbing drying process Chiren'urea) finish to 1 liter with 0.8g water "heat treatment of the support" above subbed support, the support is heated at 140 ° C., then slowly cooled. It was conveyed at a tension of 1 × 10 ⁵ Pa at that time.

(Back layer surface side coating) The back layer coating solution 4 and the back protective layer coating solution 4 having the following compositions were respectively filtered using a filter having a quasi-absolute filtration accuracy of 20 μm before coating, and then prepared by an extrusion coater. A total wet film thickness of 30 was formed on the antistatically processed undercoat layer B-3 of the support.
Coating was performed simultaneously at a rate of 120 m / min to a thickness of 120 μm, followed by drying at 60 ° C. for 4 minutes.

[0168] [Coating Solution for Back Layer 4] Methyl ethyl ketone 16.4 g / m ² polyester resin (Bostic Co., Vitel PE2200B) 106mg / m ² infrared dye -C 37 mg / m ² stabilizer B-1 (manufactured by Sumitomo Chemical Co. Sumilizer BPA) 20 mg / m ² stabilizer B-2 (Yoshitomi Pharmaceutical Tomisorb 77) 20 mg / m ² cellulose acetate propylate (Eastman Chemical Company CAP504-0.2) 1.0 g / m ² cellulose acetate butyrate (Eastman Chemical Company) CAB381-20) 1.0 g / m ² [Back protective layer coating solution 4] Methyl ethyl ketone 22 g / m ² polyester resin (Bostic, Vitel PE2200B) 106 mg / m ² Antistatic agent; (CH ₃ ) ₃ SiO — [(CH _{3) 2} S iO] ₂₀ - _{[CH 3 SiO {CH 2 CH 2} CH 2 O (CH 2 CH 2 O) 10 (CH 2 CH 2 CH 2 O) 15 CH 3} ] _{30 - Si (CH 3) 3} 22mg / m 2 Fluorinated surfactant F-1: C ₈ F ₁₇ SO ₃ Li 10 mg / m ² Cellulose acetate propylate (CAP504-0.2 from Eastman Chemical) 1.0 g / m ² Cellulose acetate butyrate (CAB381- from Eastman Chemical) 20) 1.0 g / m ² matting agent (Shiroid 74, Fuji Devison, Inc .; silica having an average particle size of 7 μm) 17 mg / m ² (Preparation of photosensitive layer) << Preparation of photosensitive silver halide emulsion E >> A1 Phenylcarbamoyl gelatin 88 0.3 g Compound (A) (10% methanol solution) 10 ml Potassium bromide 0.32 g To 5429 ml with water Finish B1 0.67 mol / L silver nitrate aqueous solution 2635 ml C1 Potassium bromide 51.55 g Potassium iodide 1.47 g Finish with water 660 ml D1 Potassium bromide 154.9 g Potassium iodide 4.41 g Iridium chloride (1% solution) 0 .93 ml E1 0.4 mol / l aqueous potassium bromide solution Silver potential control amount below F1 56% aqueous acetic acid solution 16.0 ml G1 anhydrous sodium carbonate 1.72 g Finish up to 151 ml with water Compound (A): HO (CH ₂ CH ₂ O) ) _N- [CH (C
_{H 3) CH 2 O] 17} - (CH 2 CH 2 O) m H m + n =
5-7 The solution (B1) was added to the solution (A1) using a mixing stirrer shown in JP-B-58-58288 and JP-B-58-58289.
Of the solution (C1) at 45 ° C. and pAg8.
While controlling to 09, the addition was carried out by the simultaneous mixing method in 4 minutes and 45 seconds to form nuclei.

After a lapse of 7 minutes, the rest of the solution (B1) and the whole amount of the solution (D1) were added over 14 minutes and 15 seconds by a double jet method while controlling the temperature at 45 ° C. and the pAg at 8.09. During the mixing, the pH of the reaction solution was 5.6.

After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (F1) was added to precipitate a silver halide emulsion. The supernatant was removed, leaving 2000 ml of sedimentation,
After adding 10 L of water and stirring, the silver halide was precipitated again. The supernatant was removed, leaving 1500 ml of the sedimented portion, and 10 L of water was further added. After stirring, the silver halide was sedimented. After removing the supernatant liquid leaving 1500 ml of the sedimented portion, the solution (G1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and water was added so as to be 1161 g per mol of silver.

This emulsion had an average grain size of 0.058 μm.
m, coefficient of variation of particle size 12%, [100] face ratio 9
It was 2% monodispersed cubic silver iodobromide grains.

Further, the obtained grains were chemically sensitized with 2 × 10 ^-4 mol of sodium thiosulfate per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3.
a, 7-Tetrazaindene was added.

<< Preparation of Powdered Organic Silver Salt E >> Behenic acid 130.8 g and arachidic acid 67.7 in 4720 ml of pure water.
g, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 mol sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution.
While maintaining the temperature of the above-mentioned sodium fatty acid solution at 55 ° C., 31.7 g of the above-mentioned photosensitive silver halide emulsion E and 465 ml of pure water were added, and the mixture was stirred for 5 minutes.

Next, 702.6 ml of a 1M silver nitrate solution was added to 2
And the mixture was stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and draining are repeated until the conductivity of the waste water becomes 2 μS / cm, and centrifugal dehydration is performed. Then, the drying machine is used with a flash-type drier flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.). Inlet hot air temperature 7
Drying was performed under a 5 ° C. operating condition until the water content became 0.1% to obtain a powdered organic silver salt E. At this time, the dry hot air used was heated air in the atmosphere with an electric heater. An infrared moisture meter was used to measure the water content of the organic silver salt composition.

<< Preparation of Preliminary Dispersion E >> Polyvinyl butyral powder (Butvar B- manufactured by Monsanto)
79) with 14.57 g of methyl ethyl ketone (hereinafter referred to as MEK).
Dissolved in 1457 g, VMA-GETZMAN
Preliminary dispersion liquid E was prepared by gradually adding 500 g of the powdered organic silver salt E while stirring with a disperser DISPERMAT CA-40M manufactured by Company N and thoroughly mixing.

<< Preparation of Photosensitive Emulsion Dispersion E >> 0.5 mm diameter zirconia beads (Toray Toraycele, manufactured by Toray Industries Co., Ltd.) were added to the preliminary dispersion E using a pump such that the residence time in the mill was 10 minutes using a pump. Media type disperser DI filled with 80%
SPERMAT SL-C12EX type (VMA-GET
ZEMNN) and dispersed at a mill peripheral speed of 13 m / s to prepare a photosensitive emulsion dispersion E.
After the dispersion, the organic silver salt particles were observed with an electron microscope photograph. 3
As a result of measuring the particle size and thickness of 00 organic silver salt particles, 2
05 were monodispersed tabular organic silver salts having an AR of 3 or more and a dispersity of 25%. Incidentally, the average particle size was 0.7 μm.
When the organic silver salt particles were similarly observed after coating and drying,
The same particles could be confirmed.

<< Preparation of Stabilizer Liquid >> 0.9 g of Stabilizer 1,
0.28 g of potassium acetate was dissolved in 10.1 g of methanol to prepare a stabilizer solution.

<< Preparation of infrared sensitizing dye liquid >> 29 mg of infrared sensitizing dye 1, 4.5 g of 2-chloro-benzoic acid, 8.4
g of Stabilizer 2 and 280 mg of 5-methyl-2-mercaptobenzimidazole were dissolved in 77.2 ml of MEK in the dark to prepare an infrared sensitizing dye solution. << Preparation of additive liquid a-1 >> 107 g of reducing agent A-4, 4.
8 g of 4-methylphthalic acid, 1 g of compound 21, 0.7
4 g of infrared dye-C was dissolved in 260 g of MEK,
It was set to -1.

<< Preparation of Additive Solution b-1 >> 11.6 g of antifoggant 2 and 10 g of acid anhydride 4-11 were added to MEK126.
g) to give an additive liquid b-1.

<< Preparation of Additive Solution c >> 21 g of an alkoxysilane compound: Ph-NH- (CH
₂₎ -Si- (OCH _{3) 3} was used as additive solution c was dissolved in MEK of 204 g.

<< Preparation of Photosensitive Layer Coating Solution E >> The photosensitive emulsion dispersion E (1641 g) and MEK 506 g were kept at 21 ° C. while stirring, and 10.75 g of antifoggant 1 (11.2% methanol solution) was added. The mixture was stirred for 1 hour.
Further, calcium bromide (11.2% methanol solution) 1
3.6 g was added and stirred for 20 minutes. When the silver halide therein was observed with an electron microscope, silver halide grains of less than 0.01 μm could be observed. The silver halide grains were observed with an electron microscope photograph. When the particle size of 500 organic silver salt particles was measured, the number of particles having a particle size of less than 0.01 μm was 45% of the total number of silver halide particles.

Subsequently, 11.3 g of a stabilizer liquid was added to add 1
After stirring for 0 minutes, 90.5 g of an infrared sensitizing dye solution was added, followed by stirring for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While maintaining the temperature at 13 ° C, polyvinyl butyral (Monsanto Butvar)
B-79) 349.6 g was added and stirred for 30 minutes, and then 5-methyl-2-mercaptobenzimidazole 9 was added.
5 mg and 3.5 g of tetrachlorophthalic acid were added and 30
Stirred for minutes. Then, 1.2 g of 5-nitroindazole, 0.4 g of 5-nitrobenzimidazole, the toning agent as shown in Table 2, the amount shown in Table 2, and MEK24
2 g were added. While further stirring, the additive liquid a-1
373.5 g, 148.6 g of the additional solution b-1 and 225 g of the additional solution c were sequentially added and stirred to obtain a photosensitive layer coating solution E.

[0183]

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[0184]

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<< Preparation of Matting Agent Dispersion 7 >> Monodisperse silica 30 having an average particle diameter of 6 μm was added to 1.7 g of MEK per 1 m ^2.
mg and 8000 with a dissolver-type homogenizer.
This was dispersed at 30 rpm for 30 minutes to prepare a matting agent dispersion liquid 7.

[0186] "Preparation of additive solution d" 1m ² per 0.17
g of phthalazine was dissolved in MEK of 2.73 g per 1 m ^{2 to} obtain an additive liquid d.

<< Preparation of Surface Protective Layer Coating Solution 7 >> While stirring 15.9 g of MEK per 1 m ² , cellulose acetate butyrate (Eastman Chemical) was used.
CAB171-15): 1.8 g, polymethylmethacrylic acid (Rohm & Haas Company, Paraloid A-21):
85 mg, benzotriazole: 20 mg, the amount of the compound of the general formula (3) as shown in Table 2 shown in Table 2, the silicon-based antistatic agent AS-1: (CH ₃ ) ₃ SiO — [(C
_{H 3) 3 SiO] 20 -} [(CH 3 SiO-CH 2 CH 2 CH 2
O) (CH ₂ CH ₂ O) ₆ (CH ₂ CH ₂ CH ₂ O) ₆ CH ₂ C
_{H 2 O 20] -OSi (CH} 3) was added 320mg dissolution. Next, 1.75 g of the matting agent dispersion liquid 7 and the additive liquid d
2.9 g were added sequentially and stirred to prepare a surface protective layer coating solution 7.

<< Coating on the Photosensitive Layer >> The viscosity of the coating solution for the photosensitive layer and the coating solution for the surface protective layer was adjusted to 0.228 Pa · s and 0.184 Pa · s by adjusting the amount of the solvent.
Each coating solution is passed through a filter having a quasi-absolute filtration accuracy of 20 μm, filtered, discharged from a slit of an extrusion die coater, laminated, and overlaid on the undercoat layer A-3 at a speed of 90 m / min. At the same time. Eight seconds later, the film is dried for 5 minutes using hot air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C., and then wound into a roll at an ambient temperature and humidity of 23 ° C., 50% RH, and a tension of 196 N / m (20 kg / m). The photosensitive materials shown in Table 2 were produced. The photosensitive layer of the obtained photosensitive material had a coated silver amount of 1.5 g / m ² and the surface protective layer had a dry film thickness of 2.5 μm.

The amount of the remaining solvent methyl ethyl ketone (MEK) in the obtained sample was 70 mg / m ² . The Vickers hardness of the surface of the sample 202 on the image forming layer side was 100. The obtained sample was subjected to 25 ° C., 60%
After humidifying for 24 hours in the RH environment, 46.3 cm ² of the film area was cut out under the same atmosphere, the mass was measured, and this was finely cut into about 5 mm and stored in a special vial, and the septum and aluminum were removed. After sealing with a cap,
The sample was set on a Hewlett-Packard HP7694 headspace sampler, the headspace sampler was heated at 120 ° C. for 20 minutes, and the evaporated water was quantified by the Karl Fischer method to determine the equilibrium water content of the sample.
Sample 202 was 0.7%.

Evaluation was performed in the same manner as in Example 1. Table 2 shows the above process and results.

[0191]

[Table 2]

As is clear from Table 2, the sample of the present invention is superior to the comparative sample in all evaluation items.

[0193]

According to the present invention, it is possible to provide a photothermographic material and a processing method for the photothermographic material, which have less fog during raw storage, are less likely to be softened and have lower density, and are less likely to cause development unevenness during raw storage. .

[Brief description of the drawings]

FIG. 1 is a side view illustrating a configuration example of a heat developing machine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermal developing machine 2 Thermal developing photosensitive material 3 Carry-in roller pair 4 Carry-out roller pair 5 Roller 6 Smooth surface 7 Heater 8 Guide plate

Claims (7)

[Claims] 1. A photothermographic material having an organic silver salt, a silver halide and a reducing agent on one side of a support, wherein a high contrast agent is provided on the support having a silver halide and a compound represented by the following general formula: A photothermographic material comprising the compound represented by (1) or (2). Formula (1) Rf °-(O-Rf ′) _n1 -L′-X ′ _m1 [wherein, Rf ° represents an alkyl group, an aryl group or an alkenyl group containing at least one fluorine atom.
Rf 'represents an alkylene group containing at least one fluorine atom. L 'represents a simple bond or a divalent linking group, and X' represents a hydroxy group, an anionic group or a cationic group. n1 and m1 each represent an integer of 1 or more. General formula (2) [(Rf "O) _n2- (PFC) -CO-Y] _k- L" -X " _{m2 wherein} Rf" represents a perfluoroalkyl group having 1 to 4 carbon atoms. And n2 represents an integer of 1 to 5. (PF
C) represents a perfluorocycloalkylene group. Y represents a linking group containing an oxygen atom or a nitrogen atom, L ″ represents a mere bond or a divalent linking group, X ″ represents an anionic group,
It represents a water-solubilizing polar group containing a cationic group, a nonionic group or an amphoteric group. k represents an integer of 1 to 3, m2 represents 1 to 5
Represents an integer. ] 2. A photothermographic material comprising an organic silver salt, a silver halide and a reducing agent on one side of a support, wherein a high contrast agent and a compound represented by the following general formula (1) are provided on the support having a silver halide. (3) A photothermographic material comprising the compound represented by (3). Embedded image [Wherein, Rf represents an alkyl group containing at least one fluorine atom, L ₁ and L ₂ each represent a simple bond or a linking group, and X represents a hydrogen atom, a hydroxy group, an anionic group, a cationic group. And R ₁ and R ₂ each represent a hydrogen atom or a lower alkyl group. m and n each represent a polymerization molar ratio, and m + n =
1.0 and p represents an integer of 1 or more. ] 3. The method of claim 1, wherein the toning agent is represented by the following general formula (N-1):
3. The photothermographic material according to claim 1, which is a compound represented by (N-2) or (N-3). Embedded image [In the general formula (N-1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (N-1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. General formula (N-
In 2), R ⁴ represents a substituent. General formula (N-
In 3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group. A heterocyclic thio group or a heterocyclic amino group. In the general formula (N-3), X and Y or A and B may be bonded to each other to form a cyclic structure. ] 4. When the photothermographic material is subjected to thermal development processing by a thermal developing machine, the surface having silver halide is brought into contact with a roller to drive the roller, and the silver halide is applied to the support. The photothermographic material according to any one of claims 1 to 3, wherein the surface opposite to the side having the surface is brought into contact with a smooth surface, slid and conveyed, and subjected to heat development processing. 5. The photothermographic material according to claim 4, wherein the transport speed at the time of transport and thermal development processing is 22 to 40 mm / sec. 6. When the photothermographic material according to claim 1, 2 or 3 is thermally developed by a thermal developing machine, the surface having silver halide is brought into contact with the roller to drive the roller, and A method for processing a photothermographic material, wherein the surface opposite to the side having silver halide with respect to the support is brought into contact with a smooth surface, slid, transported, and subjected to thermal development processing. 7. The method for processing a photothermographic material according to claim 6, wherein the transport speed during the transport and thermal development processing is 22 to 40 mm / sec.