JP2002287300A - Silver halide photographic sensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for plate making less liable to silver stain in development and a processing method for the material and to provide a silver halide photographic sensitive material for plate making less liable to silver stain even in mass processing under low replenishment and in rapid processing and a processing method for the material. SOLUTION: Each of the silver halide photographic sensitive materials has at least one photosensitive silver halide emulsion layer on one face of the base, contains a compound of the formula Rf-(L1 )m -(Y1 )n -X, Rf-(O-Rf')n1 -L2 -X'm1 or [(Rf'O)n2 -(PFC)-CO-Y2 ]k -L3 -X"m2 and further contains a compound of formula [II-1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a photographic light-sensitive material or a light-sensitive material) suitable for printing plate making and a method for processing a silver halide photographic light-sensitive material. The present invention also relates to a silver halide photographic material and a method for processing a silver halide photographic material which are less likely to be stained during development.

[0002]

2. Description of the Related Art In recent years, in the silver halide photographic light-sensitive material market for printing plate making, a screening method for forming an image with a smaller halftone dot than before, such as high-definition screening or FM screening, has begun to spread. For such a screening method, a hard type photosensitive material in which the density of minute dots is easy to be applied is preferable.

[0003] As such a high contrast type photographic material, a rapid access type photographic material having high gamma characteristics is usually used, but from the viewpoint of high contrast, a hydrazine derivative is converted to a halogen. For example, US Pat. No. 4,269,
No. 929, or JP-A No. 4-9 containing a nucleation accelerator.
Ultra-high contrast type photographic light-sensitive materials such as No. 8239 are more preferably used. However, the developing solution of the photographic material contains a compound having a dissolving effect on silver halide such as a sulfite, and a large amount of silver complex is eluted from the photographic material in the developing solution. Occur.
The silver complex eluted in the developing solution is reduced by the developing agent, and silver is deposited and accumulated in a developing tank, a vat, a developing tank of an automatic developing machine, a roller, and the like. This is also referred to as silver stain or silver sludge, which adheres to the photosensitive material to be processed and stains the image, so that periodic cleaning and maintenance of the equipment is required. Heretofore, as a countermeasure, there has been an example in which a silver halide light-sensitive material contains a silver sludge inhibitor or the like to suppress the elution of silver, but it has not been enough to improve the adhesion of silver stain on the light-sensitive material.

In recent years, it has been desired to shorten the development time for reasons such as efficiency, environmental friendliness, and cost reduction. Conventionally, the entire processing from the insertion of the leading edge of the film into the automatic processing machine to the exit of the drying zone is required. Time (Dry to Dry) is 90
It usually took more than a second, but recently, 60
Sub-second rapid processing is required. However, in order to obtain high sensitivity by rapid processing, it is necessary to increase the activity of the developer. Therefore, if the amount of sulfite added is increased, the amount of the silver complex eluted into the developer increases, and the degree of silver contamination is increased. However, there is a drawback that the advantages of rapid processing cannot be fully utilized.

[0005] On the other hand, for reasons of environmental suitability and cost reduction, it is desired to further reduce the replenishment of the developing solution and the fixing solution. However, reducing the replenishment amount of the developer further increases the amount of the silver complex eluted into the developer and further deteriorates the degree of silver stain, which is a problem.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which is hardly stained with silver during development. It is to provide a processing method. Also, when the photosensitive material is processed in large quantities with low replenishment,
It is an object of the present invention to provide a silver halide photographic light-sensitive material for printing plate making which is hardly stained with silver even when processed quickly.

[0007]

The above object of the present invention is attained by the following constitutions.

[0008] 1. The support has at least one light-sensitive silver halide emulsion layer on one side of the support, and has the general formula [I-
1) a silver halide photographic light-sensitive material comprising a compound represented by the formula [I-2] or [I-3], and further comprising a compound represented by the formula [II-1]. material.

[0009] 2. 2. The silver halide photographic light-sensitive material according to 1, wherein the material contains a hydrazine derivative as a high contrast agent.

In processing the silver halide photographic light-sensitive material described in 3.1 or 2, the replenishing amount of the developing solution is set to 1
A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed at 30 to 150 ml per m ² and a replenishing amount of a fixing solution is 50 to 300 ml per 1 m ^{2 of the} light-sensitive material.

4. Total processing time (Dry to
(Dry) is 10 to 60 seconds.
The method for processing a silver halide photographic light-sensitive material described in the above.

5. 5. The method for processing a silver halide photographic light-sensitive material according to 3 or 4, wherein the processing is performed using a processing solution prepared from a solid processing agent.

6. 6. The method for processing a silver halide photographic light-sensitive material according to 3, 4 or 5, wherein the processing is carried out with a developer containing a developing agent represented by the general formula (A).

Hereinafter, the present invention will be described in detail. The compound represented by the formula [I-1], [I-2] or [I-3] of the present invention will be described.

In the general formulas [I-1] and [I-2], Rf represents an aliphatic group containing at least one fluorine atom, and the aliphatic group has 1 to 18 carbon atoms. It is preferable that it has 2 to 12 carbon atoms, and it is particularly preferable that it has 3 to 7 carbon atoms.

In the general formula [I-1], L ₁ represents a divalent linking group. Examples of the divalent linking group include a sulfonamide group, an alkylene oxide group, a phenoxy group and an alkylenecarbonyl group. Preferred are mentioned.

In the general formula [I-1], Y ₁ represents an alkylene oxide group or an alkylene group which may have a substituent, and examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group. And an ethylene oxide group is particularly preferred. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, and an ethylene group is particularly preferable.

In the general formula [I-1], X is a hydrogen atom,
A hydroxyl group, represents an anionic group or a cationic group, and examples of the anionic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
Preferable examples of the counter cation of the anionic group include alkali metal ions such as sodium ion and potassium ion, and ammonium ion. The cationic group is preferably a quaternary alkylammonium group, and the counter anion of the cationic group is preferably a halide ion, a p-toluenesulfonic acid ion, or the like.

In the general formula [I-1], m is 0 or 1.
Represents an integer of 5 to 5, and n represents 0 or an integer of 1 to 40. It is particularly preferable that m is 0 and n is 10 to 20.

In the general formula [I-2], Rf ′ represents an alkylene group containing at least one fluorine atom, and preferably has 1 to 8 carbon atoms, and has 2 to 5 carbon atoms.
Is more preferable, and 2 or 3 is particularly preferable.

In the general formula [I-2], L ₂ represents a mere bond or a linking group, such as an alkylene group, an arylene group, or a divalent linking group containing a hetero atom. Are preferred.

In the general formula [I-2], X 'represents a hydroxyl group, an anionic group or a cationic group, and the anionic group is preferably, for example, a carboxyl group, a sulfonic group or a phosphate group. The counter cation of the anionic group is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an ammonium ion. As the cationic group, a quaternary alkylammonium group is preferable, and as the counter anion of the cationic group, a halide ion, p-
Preferred examples include toluenesulfonic acid ions.

In the general formula [I-2], n1 and m1 each represent an integer of 1 or more, and preferably, n1 is 1 or more and 10 or less, and m1 is 1 or more and 3 or less.

In the general formula [I-3], Rf ″ represents a perfluoroalkyl group having 1 to 4 carbon atoms,
As the perfluoroalkyl group, a trifluoromethyl group is particularly preferred. In the general formula [I-3], (PFC)
Represents a perfluorocycloalkylene group, and examples of the perfluorocycloalkylene group include a perfluorocyclooctylene group, a perfluorocycloheptylene group, a perfluorocyclohexylene group, and a perfluorocyclopentylene group. And a perfluorocyclohexylene group is particularly preferred.

In the general formula [I-3], Y ₂ represents a linking group containing an oxygen atom or a nitrogen atom. As the linking group, —OCH ₂ — and —NHCH ₂ — are particularly preferable.

In the general formula [I-3], L ₃ represents a simple bond or a linking group, and the linking group is a substituted or unsubstituted alkylene group (for example, an ethylene group, a propylene group, an iso- Butylene group, etc.), arylene (for example,
A phenylene group, a methoxyphenylene group, etc.), a combination of an alkylene group and an arylene group (eg, a xylylene group), an oxydialkylene group (eg, —CH ₂ CH ₂ O)
CH ₂ CH ₂ -, etc.), Chiojiarukiren group (e.g., -
CH ₂ CH ₂ SCH ₂ CH ₂ — and the like).

In the general formula [I-3], X ″ represents a water-solubilizing polar group containing an anionic group, a cationic group, a nonionic group, or an amphoteric group. COOH, COOM, SO ₃ H, SO ₃ M, OSO _{3
H, OSO 3 M, (OCH} 2 CH 2) OSO3M, OPO
(OH) ² , OPO (OM) ² (where M is sodium,
A metal ion such as potassium or calcium, or an ammonium ion). Of these, a carboxyl group, a sulfonic acid group, and a phosphate group are preferable. As the counter cation of the anionic group, a sodium ion , Alkali metal ions such as potassium ions,
Ammonium ions and the like are preferred. The cationic group is preferably a quaternary alkylammonium group, and the counter anion of the cationic group is preferably a halide ion, p-toluenesulfonic acid ion, or the like. Further, a hydroxyl group is preferable as the nonionic group.

In the general formula [I-3], n2 represents an integer of 1 to 5, k represents an integer of 1 to 3, and m2 represents an integer of 1 to 5. Preferably, k is preferably 1 or 2, and m2 is preferably 1.

Hereinafter, the compounds represented by the general formulas [I-1] and [I
Specific examples of the compound represented by [-2] or [I-3] are shown below, but the present invention is not limited thereto.

The compound represented by the general formula [I-1] of the present invention
Specific example of product I-1-1. C₈F₁₇SO_ThreeKI-1-2. C₈F₁₇SO_ThreeLi I-1-3. C₈F₁₇COONH_Four I-1-4. C₈F₁₇COOK I-1-5. C₉F₁₉OC₆H_Four-SO_ThreeKI-1-6. C₉F₁₉OC₆H_Four-SO_ThreeNa I-1-7. C₆F₁₃OC₆H_Four-SO_ThreeKI-1-8. C₆F₁₃-C₆H_Four-SO_ThreeNa I-1-9. C₇F₁₅COONH_Four I-1-10. NaO_ThreeS (CHCOOCH_TwoCH_TwoC₈F
₁₇) (CH_TwoCOOCH_TwoCH_TwoC₈F₁₇) I-1-11. C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_TwoCO
OK) I-1-12. C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_TwoCH_Two
OPO_ThreeNa_Two) I-1-13. C₈F₁₇SO_TwoN (C₁₂H_{twenty five}) ((C_TwoH_Four
O)_Four-C_FourH₈SO_ThreeNa) I-1-14. C₆F₁₃CH_TwoCH_TwoSO_ThreeNH_Four I-1-15. CF_ThreeCF_Two(CF_TwoCF_Two)_ThreeCH_TwoCH_Two
SO_ThreeNH_Four I-1-16. CF_ThreeCF_Two(CF_TwoCF_Two)_FourCH_TwoCH_Two
SO_ThreeNH_Four I-1-17. C₆F₁₃CH_TwoCH_Two-O-PO (ON
H_Four)_Two I-1-18. C₆F_ThreeCH_TwoCH_Two-O-PO (ON
H_Four) (_OCH_TwoCH_TwoOH) 1-1-1. C_TwoF_Five(CH_Two)₆SO_ThreeNH_Four I-1-20. C_ThreeF₇(CH_Two)_FiveSO_ThreeNH_Four 1-1-1. C_TwoF_Five(CH_Two)₆COOLi I-1-22. C_ThreeF₇(CH_Two)_ThreeOC₆H_Four-SO_ThreeKI-1-23. NaO_ThreeS (CHCOO (CH_Two)₉C_ThreeF
₇) (CH_TwoCOO (CH_Two)₉C_ThreeF₇) I-1-24. C_ThreeF₇(CH_Two)_FiveSO_TwoN (C_ThreeH₇)
(CH_TwoCOOK) I-1-25. C_ThreeF₇(CH_Two)_FiveSO_TwoN (C₁₂H_{twenty five})
((C_TwoH_FourO)_Four-C_FourH₈SO_ThreeNa) 1-1-2. (C_TwoF_FiveCH_TwoO) PO (OH)_Two I-1-27. CF₇CH_TwoCH_TwoOPO (OH)_Two I-1-28. C_ThreeF₇CH_TwoCH_TwoSCH_TwoCH_TwoCOOL
i I-1-29. C₆F₁₃CH_TwoCH_TwoSCH_TwoCH_TwoCOO
Li I-1-30. (C₆F₁₃CH_TwoCH_TwoO) PO (OH)_Two I-1-31. C₆F₁₃CH_TwoCH_TwoO- (CH_TwoCH
_TwoO)_Ten-HI-1-32. C₈F₁₇CH_TwoCH_TwoO- (CH_TwoCH
_TwoO)₁₂-HI-1-33. C_TenF_{twenty one}CH_TwoCH_TwoO- (CH_TwoCH
_TwoO)₈-HI-1-34. C_FourF₉CH_TwoCH_TwoO- (CH_TwoCH_TwoO)
₂₀-HI-1-35. C_ThreeF₇CH_TwoCH_TwoO- (CH_TwoCH_TwoO)
_Ten-HI-1-36. C_ThreeF₇CH_TwoCH_TwoO- (CH_TwoCH_TwoO)
₁₂-HI-1-37. C_TwoF_FiveCH_TwoCH_TwoO- (CH_TwoCH_TwoO)
₁₅-HI-1-38. C_ThreeF₇− (CH_TwoCH_TwoO)_Two− (CH_TwoC
(OH) H-CH_TwoO)_Ten-HI-1-39. C_FourF₉-CH (CH_Three) CH_TwoO- (CH
_TwoCH_TwoO)₉-HI-1-40. C₆F₁₃− (CH_TwoCH_TwoO)_Three− (CH_Two
C (OH) H-CH_TwoO)₁₂-HI-1-41. C_ThreeF₇CH_TwoCH_TwoO- (CH_TwoCH_TwoO)
₃₁-H Specific examples of the compound represented by the general formula [I-2] of the present invention I-2-1. C_FiveF₁₁− (O-CF_Two) -O-PO (ON
a)_Two I-2-2. HC₆F₁₂− (O-CF_Two) -O-PO (O
Na)_Two I-2-3. C₈F₁₇− (O-CF_Two) -O-PO (ON
a)_Two I-2-4. C_TenF_{twenty one}− (O-CF_Two) -O-PO (O
Na)_Two I-2-5. C₁₂F_{twenty five}− (O-CF_Two) -O-PO (O
Na)_Two I-2-6. C_ThreeF₇− (OC_TwoF_Four) -O-PO (ON
a)_Two I-2-7. C_FourF₉− (OC_TwoF_Four) -O-PO (ON
a)_Two I-2-8. C_FiveF₁₁− (OC_TwoF_Four) -O-PO (O
Na)_Two I-2-9. HC₆F₁₂− (OC_TwoF_Four) -O-PO
(ONa)_Two I-2-10. C₇F₁₅− (OC_TwoF4) -O-PO
(ONa)_Two I-2-11. C₉F₁₉− (OC_TwoF_Four) -O-PO
(ONa)_Two I-2-12. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-PO
(ONa)_Two I-2-13. C_ThreeF₇− (O-CF_Two)₆-O-PO (O
Na)_Two I-2-14. C_FourF₉− (O-CF_Two)₆-O-PO (O
Na)_Two I-2-15. C_FiveF₁₁− (O-CF_Two)_Five-O-PO
(ONa)_Two I-2-16. HC₆F₁₂− (O-CF_Two)_Three-O-PO
(ONa)_Two I-2-17. C_ThreeF₇-[O- (CF_Two)_Three] -COON
a I-2-18. C_FourF₉-[O- (CF_Two)_Three] -COON
a I-2-19. C_FiveF₁₁-[O- (CF_Two)_Three] -COO
Na I-2-20. HC₇F₁₄-[O- (CF_Two)_Three] -O-
CH (COONa)_Two I-2-21. C₈F₁₇-[O- (CF_Two)_Three] -OC
H (COONa)_Two I-2-22. C_ThreeF₇-[O- (CF_Two)_Five] -COON
a I-2-23. C_FourF₉-[O- (CF_Two)_Five] -COON
a I-2-24. C_FiveF₁₁-[O- (CF_Two)_Five] -COO
Na I-2-25. C₇F₁₅-[O- (CF_Two)_Five] -COO
Na I-2-26. C_ThreeF₇− (OC_TwoF_Four)_Five-COONa I-2-27. C_FourF₉− (OC_TwoF_Four)_Two-COONa I-2-28. C_FiveF₁₁− (OC_TwoF_Four)_Two-COONa I-2-29. HC₇F₁₄− (OC_TwoF_Four)_Two-COON
a I-2-30. C₉F₁₉− (OC_TwoF_Four)_Two-COONa I-2-31. C_TwoF_Five− (OC_TwoF_Four)_Three-COONa I-2-32. C_TwoF_Five− (OC_TwoF_Four)_Five-COONa I-2-33. C_ThreeF₇− (OC_TwoF_Four)_Four-COONa I-2-34. C_FourF₉− (OC_TwoF_Four)_Three-COONa I-2-35. C_FiveF₁₁− (OC_TwoF_Four)_Three-NHCOC
H (COONa)_Two I-2-36. HC₆F₁₂− (OC_TwoF_Four)_Three-NHCO
CH (COONa)_Two I-2-37. C_FourF₉− (OC_TwoF_Four)_Two-OCF_TwoCO
ONa I-2-38. C_FiveF₁₁− (OC_TwoF_Four)_Two-OCF_TwoC
OONa I-2-39. C₇F₁₅− (OC_TwoF_Four)_Two-OCF_TwoC
OONa I-2-40. C_FourF₉-OCF_Two-[O- (CF_Two)_Five]
-COOK I-2-41. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five]
-COOK I-2-42. HC₆F₁₂-OCF_Two-[O- (C
F_Two)_Five] -COOK I-2-43. C_FourF₉− (OC_TwoF_Four)_Five-[O- (C
F_Two)_Three] -COOK I-2-44. C_FiveF₁₁− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK I-2-45. C₆F₁₃− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK I-2-46. C₁₂F_{twenty five}− (O-CF_Two) -O-SO_ThreeN
a I-2-47. C₇F₁₅− (OC_TwoF_Four) -OC_ThreeH₆−
SO_ThreeNa I-2-48. C_FourF₉− (O-CF_Two)₆-O-SO_ThreeN
a I-2-49. HC_FiveF_Ten− (O-CF_Two)_Five-OC_ThreeH₆
-SO_ThreeNa I-2-50. HC₆F₁₂− (O-CF_Two)_Three-O-SO_Three
Na I-2-51. C_FiveF₁₁− (OC_TwoF_Four)_Two-OC_ThreeH₆−
SO_ThreeNa I-2-52. C₇F₁₅− (OC_TwoF_Four)_Two-O-SO_Three
Na I-2-53. C_ThreeF₇− (OC_TwoF_Four)_Four-OC_ThreeH₆−
SO_ThreeNa I-2-54. C_FourF₉− (OC_TwoF_Four)_Three-O-SO_ThreeN
a I-2-55. HC_FiveF_Ten− (OC_TwoF_Four)_Three-OC_ThreeH₆
-SO_ThreeNa I-2-56. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five]
-O-SO_ThreeNa I-2-57. C_FourF₉− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -O-SO_ThreeNa I-2-58. (HCF_Two)_ThreeC- (OC_TwoF_Four)_Three-O
-SO_ThreeNa I-2-59. (CF_Three)_TwoCFCF_TwoCF_Two− (O-CF
_Two)_Five-OC_ThreeH₆-SO _ThreeNa I-2-60. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-SO_Three
Na I-2-61. C_FourF₉− (OC_TwoF_Four)_Three-NHCO-
(CH_Two)_Three-N⁺(CH _Three)_Three・ Br^- I-2-62. C_FiveF₁₁− (OC_TwoF_Four)_Two-NHCO-
(CH_Two)_Three-N⁺(CH_Three)_Three・ Br^- I-2-63. HC₆F₁₂− (OC_TwoF_Four)_Two-NHCO
− (CH_Two)_Three-N⁺(CH_Three)_Three・ Br^- I-2-64. C_FourF₉− (OC_TwoF_Four)_Three-O-CH_Two−
N⁺(CH_Three)_Two(C_TwoH _FourOH) ・ Br^- I-2-65. C_FiveF₁₁− (OC_TwoF_Four)_Two-O-CH_Two
-N⁺(CH_Three)_Two(C_TwoH_FourOH) ・ Br^- I-2-66. HC₆F₁₂− (OC_TwoF_Four)_Two-O-CH
_Two-N⁺(CH_Three)_Two(C _TwoH_FourOH) ・ Br^- I-2-67. C_FiveF₁₁-OCF_Two− (OC_TwoF_Four) -N
HCO- (CH_Two)_Three-N⁺(CH_Three)_Three・ Br^- I-2-68. (CF_Three)_ThreeC- (OC_TwoF_Four)_Three-O-
CH_Two-N⁺(CH_Three)_Two(C_TwoH_FourOH) ・ Br^- I-2-69. C₁₂F_{twenty five}− (O-CF_Two) -OH I-2-70. C₇F₁₅− (OC_TwoF_Four) -OH I-2-71. C_FourF₉− (O-CF_Two)₆-OC_ThreeH₆-O
HI-2-72. C_FiveF₁₁− (O-CF_Two)_Five-OC_ThreeH₆−
OH I-2-73. HC₆F₁₂− (O-CF_Two)_Three-OH I-2-74. C_FiveF₁₁− (OC_TwoF_Four)_Two-OC_ThreeH₆−
OH I-2-75. C₇F₁₅− (OC_TwoF_Four)_Two-OC_ThreeH₆−
OH I-2-76. C_ThreeF₇− (OC_TwoF_Four)_Four-OC_ThreeH₆−
OH I-2-77. HC_FourF₈− (OC_TwoF_Four)_Three-OC
(C_TwoH_FourOH)_Three I-2-78. C_FiveF₁₁− (OC_TwoF_Four)_Three-OC_ThreeH₆−
OH I-2-79. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five]
-OH I-2-80. C_FourF₉− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -OH I-2-81. (CF_Three)_ThreeC- (OC_TwoF_Four)_Three-OH I-2-82. (HCF_Two)_TwoCFCF_TwoCF_Two− (OC
F_Two)_Five-OH I-2-83. C₁₁F_{twenty three}− (OC_TwoF_Four)_FourOH
For details, see Tokuhyo Heihei 10-500950 and 11-504
360 can be referred to.

The compound represented by the general formula [I-3] of the present invention
Specific example of product I-3-1. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourCOO^- I-3-2. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- I-3-3. (CF_ThreeO) (PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- I-3-4. (CF_ThreeO)_Three(PFC) -CON (C_ThreeH₆
SO_Three ^-) C_ThreeH₆N⁺(CH_Three)_TwoHI-3-5. (CF_ThreeO) (PFC) -CON (C_ThreeH₆
SO_Three ^-) C_ThreeH₆N⁺(CH_Three)_TwoHI-3-6. [(CF_ThreeO)_Three(PFC) -COOC
H_Two]_TwoCH-CONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three
^- I-3-7. [(CF_ThreeO)_Two(PFC) -COOC
H_Two]_TwoCH-CONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three
^- I-3-8. [(CF_ThreeO) (PFC) -COOCH_Two]
_TwoCH-CONHC_ThreeH ₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- I-3-9. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆
N⁺(CH_Three)_TwoC_TwoH_FourOH ・ Cl^- I-3-10. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoC_TwoH _FourOH ・ Cl^- I-3-11. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆N⁺(CH_Three)_TwoC_TwoH_FourOH ・ Cl^- I-3-12. (CF_ThreeO)_Three(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-13. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-14. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-15. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- I-3-16. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- I-3-17. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) N⁺(CH_Three)_TwoH ・ Cl^- I-3-18. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-19. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-20. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoCHC_ThreeH₆N⁺(CH_Three)_TwoH ・ Cl^- I-3-21. (CF_ThreeO)_Three(PFC) -COO (C_Two
H_FourO)₁₂HI-3-22. (CF_ThreeO)_Two(PFC) -COO (C_Two
H_FourO)₁₂HI-3-23. (CF_ThreeO) (PFC) -COO (C_TwoH
_FourO)₁₂HI-3-24. (CF_ThreeO)_Three(PFC) -COO (C_Two
H_FourO)₁₅CH_Three I-3-25. (CF_ThreeO)_Two(PFC) -COO (C_Two
H_FourO)₁₅CH_Three I-3-26. (CF_ThreeO) (PFC) -COO (C_TwoH
4O)₁₅CH_Three I-3-27. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆OH I-3-28. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆OH I-3-29. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoCHC_ThreeH₆OH I-3-30. (CF_ThreeO)_Three(PFC) -CONHC_Three
H₆COONa I-3-31. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆COONa 1-3-3-32. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆COOK I-3-33. (CF_ThreeO)_Three(PFC) -CONHC_Three
H₆SO_ThreeNaI-3-34. (CF_ThreeO)_Two(PFC) -CONHC_Three
H₆SO_ThreeNaI-3-35. (CF_ThreeO) (PFC) -CONHC_ThreeH
₆SO_ThreeKI-3-36. (CF_ThreeO)_Three(PFC) -CON (C_Three
H₆SO_ThreeNa) C_ThreeH₇ I-3-37. (CF_ThreeO)_Two(PFC) -CON (C_Three
H₆SO_ThreeNa) C_ThreeH₇ I-3-38. (CF_ThreeO) (PFC) -CON (C_ThreeH
₆SO_ThreeNa) C_ThreeH₇ I-3-39. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) COONa I-3-40. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) COONa I-3-41. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) COONa I-3-42. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (COONa) _Two I-3-43. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (COONa) _Two I-3-44. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (COONa)_Two I-3-45. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoC (CH_Three) SO_ThreeNaI-3-46. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoC (CH_Three) SO_ThreeNaI-3-47. [(CF_ThreeO) (PFC) -COOC
H_Two]_TwoC (CH_Three) SO_ThreeNaI-3-48. [(CF_ThreeO)_Three(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆SO_ThreeNaI-3-49. [(CF_ThreeO)_Two(PFC) -COOCH
_Two]_TwoCHC_ThreeH₆SO_ThreeNaI-3-50. [(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,
4th and 5th place, (CF_ThreeO)_TwoIn the third and fourth places
(CF_ThreeIn the case of O), it is the fourth place.

For the method for synthesizing the compound represented by the above formula [I-3], reference can be made to JP-A-10-158218 and JP-T-2000-505803.

Next, the compound represented by the general formula [II-1] of the present invention will be described. In the general formula [II-1], examples of the heterocycle containing a nitrogen atom represented by Z include oxazole, benzoxazole, thiazole, benzothiazole, triazine, pyrimidine, tetrazaindolizine, triazaindene, and purine. And preferably a heterocyclic ring containing a 5- to 6-membered nitrogen atom to which a benzene ring may be condensed. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a cation such as a substituted or unsubstituted ammonium ion. Further, the heterocyclic ring is represented by -SM in the general formula [II-1].
It may have a substituent other than a group, and examples of the substituent include a halogen atom, a sulfo group, a hydroxyl group, a lower alkyl group, and a phenyl group.

Specific examples of the compound represented by the formula [II-1] are shown below, but the present invention is not limited thereto.

[0035]

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[0036]

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In the present invention, the compound represented by the general formula [II-1] is preferably a compound represented by the general formulas [A] to [C].

First, the compound represented by the formula (A) will be described.

[0039]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group,
Aryl group, aralkyl group, hydroxy group, mercapto group, carboxy group, sulfo group, phosphono group, amino group,
It represents a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxy group.

An alkyl group, an aryl group, an aralkyl group,
The amino group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the sulfamoyl group, and the alkoxy group may further have a substituent, and the substituent may be the same as those described for R ₁ and R _2. Can be mentioned. Further, R ₁ and R ₂ may be linked to form a ring.
R _1, R ₁ Preferred examples of R _2, either one of R ₂ is an alkyl group which may have a substituent group having 1 to 10 carbon atoms, have a substituent group having 6 to 12 carbon atoms And an aralkyl group which may have a substituent having 7 to 12 carbon atoms, a nitro group, a cyano group, and a halogen atom. A case where R ₁ and R ₂ are linked to form a saturated 5- to 6-membered ring is also a preferred example.

As more preferred examples of R ₁ and R ₂ , R ₁
Is a hydrogen atom or an alkyl group having an amino group (dimethylamino group, diethylamino group, etc.) or a heterocyclic ring (morpholino group, N-methylpiperazinyl group, pyrrolidinyl group, piperidinyl group, etc.) as a substituent. And R ₂ include an alkyl group which may have a substituent having 1 to 10 carbon atoms and an aryl group which may have a substituent having 6 to 12 carbon atoms. Specifically R
Examples of ₁ include a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperazinylmethyl group, and a pyrrolidinylmethyl group. A methyl group as R ₂ ,
Examples include an ethyl group, a phenyl group, and a p-methoxyphenyl group.

The compounds represented by formula (A) are specifically shown below, but the present invention is not limited thereto.

[0044]

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[0045]

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Next, the compound represented by the formula (B) will be described.

[0047]

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In the general formula [B] used in the present invention, Z ₂₁ and Y ₂₁ each represent an unsaturated 5-membered or 6-membered ring (for example, benzene, pyrrole, imidazole, pyrazole, pyridamine, Pyrimidine, etc.), containing three or more nitrogen atoms in combination with Z and Y, and having at least one mercapto group as a substituent. The compound represented by the general formula [B] may have a substituent other than a mercapto group, and the substituent includes a halogen atom (eg, fluorine, chlorine, bromine atom), a lower alkyl group (substituted Groups, especially those having 5 or less carbon atoms, such as methyl group and ethyl group), and lower alkoxy groups (including those having substituents, especially 5 carbon atoms such as methoxy, ethoxy, butoxy, etc.) Are preferable.), A hydroxy group, a sulfo group, a lower allyl group (including those having a substituent, and particularly preferably those having 5 or less carbon atoms), an amino group, and a COOM ₂₁ group (M ₂₁ is the above-mentioned general formula. The same as M of [II-1]), carbamoyl group, phenyl group and the like. In particular, a hydroxy group, a COOM ₂₁ group,
It preferably has an amino group or a sulfo group.

Further, compounds represented by the following general formulas [a] to [f] in the general formula [B] are particularly preferred.

[0050]

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In the formula, R ₂₁ , R ₂₂ and R _{23 each} represent a halogen atom, a lower alkyl group (including those having a substituent, preferably a methyl group, an ethyl group or the like having 5 or less carbon atoms) or lower. Alkoxy group (including those having a substituent, particularly those having 5 or less carbon atoms), hydroxy group, sulfo group, and lower allyl group (including those having a substituent, particularly those having 5 or less carbon atoms) ), An amino group, a COOM ₂₁ group (M ₂₁ has the same meaning as M in the general formula [II-1]), a carbamoyl group, and a phenyl group, and at least one is a mercapto group. In particular, the substituent other than the mercapto group in the compound represented by the general formula [a] is preferably a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group.

[0052]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ represent a halogen atom, a lower alkyl group (including those having a substituent).
Those having 5 or less carbon atoms such as a methyl group and an ethyl group are preferred. ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, particularly those having 5 or less carbon atoms) Is preferred.), An amino group, a COOM ₂₁ group (M ₂₁ has the same meaning as M in the general formula [II-1]), a carbamoyl group, and a phenyl group, and at least one is a mercapto group. Particularly, the substituent other than the mercapto group of the compound represented by the general formula [b] is preferably a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group.

[0054]

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In the formula, R ₂₁ and R ₂₂ are a halogen atom, a lower alkyl group (including those having a substituent, and particularly preferably those having 5 or less carbon atoms such as a methyl group and an ethyl group),
Lower alkoxy groups (including those having a substituent, particularly those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, particularly those having 5 or less carbon atoms) Preferred)), amino group, COO
M ₂₁ groups (M ₂₁ has the same meaning as M in the formula [II-1]), a carbamoyl group and a phenyl group, and at least one is a mercapto group. In particular, as the substituent other than the mercapto group of the compound represented by the general formula (c), a hydroxy group,
It is preferably a COOM ₂₁ group, an amino group, or a sulfo group.

[0056]

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In the formula, R ₂₁ and R _{22 each} represent a halogen atom, a lower alkyl group (including those having a substituent, and particularly preferably those having 5 or less carbon atoms such as a methyl group and an ethyl group),
Lower alkoxy groups (including those having a substituent, particularly those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, particularly those having 5 or less carbon atoms) Preferred)), amino group, COO
M ₂₁ group (M ₂₁ is the same meaning as M in the general formula [II-1]), a carbamoyl group, a phenyl group, at least one mercapto group. In particular, as the substituent other than the mercapto group of the compound represented by the general formula (d), a hydroxy group,
It is preferably a water-soluble group such as a COOM ₂₁ group, an amino group, or a sulfo group.

[0058]

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Where R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}Is a haloge
Atom, lower alkyl group (including those having a substituent,
Particularly, those having 5 or less carbon atoms such as methyl group and ethyl group are preferred.
New ), Lower alkoxy groups (including those having a substituent)
In particular, those having 5 or less carbon atoms are preferred. ), Hydroxy
Si, sulfo, lower allyl (substituted
In particular, those having 5 or less carbon atoms are preferable. ),amino
Group, COOM_{twenty one}Group (M _{twenty one}Is the same as M in the general formula [II-1].
Synonymous), carbamoyl group and phenyl group, at least
One is a mercapto group. In particular, the general formula [e]
As a substituent other than the mercapto group of the compound to be
Roxy group, COOM_{twenty one}Group, amino group or sulfo group
Preferably.

[0060]

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Where R_{twenty one}, R_{twenty two}, R_{twenty three}Is a hydrogen atom,
-SM_{twenty one}Group, hydroxy group, lower alkoxy group, -CO
OM_{twenty two}Group, amino group, -SO_ThreeM_{twenty three}Base or lower alkyl
R_{twenty one}, R_{twenty two}, R_{twenty three}At least one of
The -SM_{twenty one}Having a group. M _{twenty one}, M_{twenty two}, M_{twenty three}Is hydrogen
Atom, alkali metal atom or ammonium group,
They may be the same or different.

[0062] In the above general formula [f], R _21,
The lower alkyl group and the lower alkoxy group represented by R ₂₂ and R ₂₃ are groups each having 1 to 5 carbon atoms, and they may further have a substituent, and preferably have 1 to 3 carbon atoms. And the amino groups represented by R ₂₁ , R ₂₂ and R ₂₃ represent a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group.

In the above formula [f], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compounds represented by the general formulas [a] to [f] are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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Next, the compound represented by formula (C) will be described.

[0072]

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In the formula, Z ₃₁ and Y ₃₁ are each a ring forming an unsaturated 5- or 6-membered ring, and Z ₃₁ and Y ₃₁ together contain three or more nitrogen atoms, and It has one mercapto group as a substituent.

In the compound represented by the general formula [C],
The following compounds selected from the following general formulas [g] and [h] are preferable.

[0075]

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In the general formulas [g] and [h], R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a hydrogen atom, -SM ₃₁
Group, hydroxy group, lower alkoxy group, -COOM
₃₂ group, an amino group, -SO ₃ M ₃₃ group or a lower alkyl group, at least one of _{R 31, R 32, R 33} , R 34 has the -SM ₃₁ group. M ₃₁ , M ₃₂ and M ₃₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

[0077] The above general formula [g] and general formula _{[h], R 31, R 32, R} 33, lower alkyl and lower alkoxy groups represented by R ₃₄ are each a group having 1-5 carbon Which may further have a substituent, preferably a group having 1 to 3 carbon atoms,
The amino group represented by R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group.

The specific examples of the compounds represented by the general formulas [g] and [h] are shown below, but the present invention is not limited thereto.

Specific examples of the compound represented by the general formula [g]

[0080]

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Specific examples of the compound represented by the general formula [h]

[0082]

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In a preferred embodiment of the present invention, the high-contrast photosensitive material contains a hydrazine derivative as a high-contrast agent.

Examples of the hydrazine derivative include those represented by the following general formula (H).

[0085]

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In the formula, A is an aryl group or a sulfur atom or
Represents a heterocyclic group containing at least one oxygen atom, and G represents
-(CO) r- group, sulfonyl group, sulfoxy group, -P
(= O) R₁₆-Represents a group or an iminomethylene group, and r represents
Represents an integer of 1 or 2; ₁, A_TwoAre both hydrogen atoms
Or one is a hydrogen atom and the other is a substituted or unsubstituted
Rukylsulfonyl group or substituted or unsubstituted acyl
R represents a hydrogen atom, each of which is substituted or unsubstituted
Alkyl group, alkenyl group, aryl group, alkoxy
Group, alkenyloxy group, aryloxy group, heterocycle
Oxy, amino, carbamoyl or oxycal
Represents a bonyl group. R₁₆Is substituted or unsubstituted respectively
Alkyl, alkenyl, alkynyl, aryl
Group, alkoxyl group, alkenyloxy group, alkynyl
Represents an oxy group, an aryloxy group, or an amino group.

Among the compounds represented by the general formula (H), the compound represented by the following general formula (Ha) is more preferred.

[0088]

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In the formula, R ₁₁ represents an aliphatic group (octyl group, decyl group, etc.), an aromatic group (phenyl group, 2-hydroxyphenyl group, chlorophenyl group, etc.) or a heterocyclic group (pyridyl group, thienyl group, furyl group, etc.). And the like, and those further substituted with a suitable substituent are preferably used. Furthermore, it is preferred for R ₁₁ contains at least one ballast group or a silver halide adsorption accelerating group.

As the ballast group, those commonly used in immobile photographic additives such as couplers are preferable, and are relatively inert to photographic properties having 8 or more carbon atoms, for example, alkyl groups, alkenyl groups, Examples include an alkynyl group, an alkoxyl group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, even if a plurality of Xs are the same, they may be different. Is also good.

In the general formula (Ha), A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula (H), and both are preferably hydrogen atoms.

In the general formula (Ha), G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and a carbonyl group is particularly preferable.

R ₁₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, allyl group, heterocyclic group, alkoxyl group, hydroxyl group, amino group, carbamoyl group or oxycarbonyl group. Preferable R ₁₂ is a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, —COOR ₁₃ group, and —CON (R ₁₄ )
(R ₁₅ ) group. R ₁₃ represents an alkynyl group or a saturated heterocyclic group; R ₁₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; and R ₁₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group. , A hydroxy group or an alkoxyl group. More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. G of R ₁₂
The electron-withdrawing group for substituting the carbon atom substituted with is preferably one having a σp value of 0.2 or more and a σm value of 0.3 or more, for example, a halogen atom, a cyano group, a nitro group, a nitroso group, a polyhaloalkyl group. Group, polyhaloaryl group, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, It represents a sulfamoyl group, a phosphino group, a phosphine oxide group, a phosphonate ester group, a phosphonamide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group.

R _{12 in the} formula (Ha) particularly preferably represents a fluorine-substituted alkyl group (monofluoromethyl, difluoromethyl, trifluoromethyl, etc.).

Specific examples of the compound represented by formula (H) are shown below, but the present invention is not limited thereto.

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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As specific examples of other preferred hydrazine compounds, see US Pat. No. 5,229,248, 4-6.
(1) to (252) described in column 0.

These hydrazine compounds can be synthesized by a known method. For example, US Pat.
No. 9,248, 59-80 column.

The amount of the hydrazine derivative to be added may be an amount which makes the contrast higher (the amount of the higher contrast). The optimum amount depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor and the like. Although different, it is generally in the range of 10 ^-6 to 10 ^-1 mole per mole of silver halide, and 10 ^-5 to 1
0 ^-2 mol is preferred.

The hydrazine derivative is added to at least one layer on the side of the silver halide emulsion layer, and is preferably a silver halide emulsion layer and / or a layer adjacent thereto, more preferably an emulsion layer. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. .2
0.8 molar equivalent, preferably 0.4 to 0.6.
Molar equivalents are more preferred. One hydrazine derivative may be used, or two or more hydrazine derivatives may be used in combination.

When the above-mentioned high contrast agent is used in the light-sensitive material to be processed, it is preferable to use a nucleation accelerator in order to promote the high contrast.

As the nucleation accelerator, the following general formula (Na)
Alternatively, a compound represented by (Nb) is preferably used.

[0116]

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In the formula (Na), R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an alkynyl group or a substituted or unsubstituted aryl group; R ₂₁ ,
R ₂₂ and R ₂₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds.

These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred examples of the adsorptive group include a heterocyclic group, a mercapto group, a thioether group, a selenoether group, a thione group, and a thiourea group.

Particularly preferred as the formula (Na) are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation accelerator (Na) will be described below.

[0121]

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[0122]

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[0123]

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[0124]

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In the above formula (Nb), Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₂₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, but Ar and R ₂₄ may be linked to form a ring.

These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide-adsorbing group include groups having the same meaning as the silver halide-adsorbing group of the compound represented by formula (H).

Specific compounds of the general formula (Nb) include the following.

[0128]

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[0129]

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Specific examples of other preferred nucleation promoting compounds include the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 17, lower right column, line 18 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and thiosulfonic acid compounds described in JP-A-1-237538.

In the present invention, the nucleation accelerator can be used in any of the photographic constituent layers on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. preferable. The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor and the like, but is generally from 10 ^-6 to 10 per mol of silver halide. ^-1 mol is preferable, and a range of 10 ^-5 to 10 ^-2 mol is particularly preferable.

The silver halide composition of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited. It is preferable to use a silver halide emulsion composed of silver chlorobromide containing 60 mol% or more of silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m, particularly 0.3 to 0.1 μm
Is preferred. The average particle size is a commonly used and easily understood term in the photographic art. The particle diameter means a particle diameter when the particle is a spherical particle or a particle that can be approximated to a sphere. When the particle is a cubic, it is converted into a sphere, and the diameter of the sphere is defined as a particle diameter. For details of the method for determining the average particle size, see Mies, James, The Theory of the Photographic Process (CE Mees &
T. H. James: The theory of
he photographic process),
Third Edition, pp. 36-43 (1966, Macmillan "Mc
millan "published by the company).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As a method of reacting the soluble silver salt with the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method in which grains are formed in the presence of excess silver ions (inverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

In the present invention, the silver halide emulsion of at least one silver halide emulsion layer contains tabular grains, and 50% of the total projected area of all grains in the emulsion layer in which the tabular grains are used. The above are preferably tabular grains having an aspect ratio of 2 or more. Particularly when the ratio of tabular grains is 60 to 7
More favorable results are obtained as the value is increased to 0% and further to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Of these tabular grains, tabular grains having a (100) plane having 50 mol% or more of silver chloride as a main plane are preferably used, and these are described in US Pat. No. 5,264,264.
No. 337, No. 5,314,798, No. 5,32
No. 0,958, and the like, and intended tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions.

In order to control the photosensitive nucleus, a transition line can be provided on the surface or inside of the tabular grains.
In order to provide a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodine ions.

The preparation of silver halide grains can be appropriately selected from acid methods, neutral methods, ammonia methods and the like. When doping metal atoms, it is particularly preferable to form particles under acidic conditions of pH 1 to 5.

As a silver halide solvent, for example, ammonia, a thioether, a thiourea compound, a thione compound, or the like can be used to control the growth of the grains during the formation of tabular grains. As thioether compounds, 3,6,9,15, described in German Patent 1,147,845
18,21-hexoxa-12-thiatricosan, 3,
9,15-trioxa-6,12-dithiaheptadecane, 1,17-dioxy-3,9-15-trioxa-
6,12-dithiaheptadecane-4,14-dione,
1,20-dioxy-3,9,12,18-tetroxa-6,15-dithiaeicosan-4,17-dione;
7,10-dioxa-4,13-dithiahexadecane-
2,15-dicarboxamide; JP-A-56-94347
And oxathioether compounds described in JP-A-1-121847; JP-A-63-259563 and JP-A-63-30.
And a cyclic oxathioether compound described in No. 1939. Particularly, thiourea is disclosed in JP-A-53-82.
No. 408 are useful, specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea, 1,3-
Examples thereof include dimethylimidazole-2-thione, 1,3-dimethylimidazole-4-phenyl-2-thione, and tetrapropylthiourea.

During physical ripening or chemical ripening, zinc, lead,
Lium, iridium, rhodium, ruthenium, osmium
Metal, palladium, platinum, etc.
Can be. In order to obtain high illuminance characteristics, iridium is
10 per mole of silver logenide ^-9-10^-3In the range of moles
Preferably. To obtain a high contrast emulsion,
Rhodium, ruthenium, osmium and / or rhenium
10 moles per mole of silver halide^-9-10^-3Mole of
It is preferable to dope in the range.

When the metal compound is added to the particles, halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, phenanthroline, or a compound thereof is added to the metal atom. Can be coordinated. The oxidation state of the metal atom can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A-2-2082, JP-A-2-20853, and JP-A-2-20853.
Examples of the hexadentate ligand and alkali complex described in JP-A Nos. 54 and 2-20855 include sodium salts, potassium salts, cesium salts and primary, secondary and tertiary amine salts. Further, a transition metal complex salt can be formed in the form of an aquo complex. For example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)] and K ₂ [RuCl ₅ (H ₂ O)]. Ru is replaced by Rh, Os, Re, I
can be replaced by r, Pd and Pt.

Rhodium, ruthenium, osmium and / or
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of uniformly distributing the particles, or a method of forming a core-shell structure and localizing a large amount in the core portion or the shell portion.

It is often better to have more of these in the shell. In addition to localization in a discontinuous layer configuration, a method may be used in which the abundance is continuously increased outside the particles. The addition amount is 1 per mol of silver halide.
The range of 0 ^-9 to 10 ^-3 mol can be appropriately selected.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Rese
arch Disclosure (hereinafter referred to as RD) 1
No. 76, 17643, pp. 22-23 (December 1978)
In the literature described or cited.

The silver halide emulsion may or may not be chemically sensitized. As a method of chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred are sulfur compounds contained in gelatin and various sulfur compounds such as thiosulfates, thioureas and rhodanines. And polysulfide compounds.

Known selenium sensitizers can be used as the selenium sensitizer. For example, U.S. Pat.
No. 499, JP-A-50-71325 and JP-A-60-150.
No. 046, etc. can be preferably used.

The light-sensitive material can contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzotriazoles, nitrobenzotriazoles,
Mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines,
Mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindene Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

It is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

In particular, it is preferable to add a polysaccharide such as dextran and dextrin described in JP-A-9-304855 in order to improve the suitability for rapid processing.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (such as vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like can be used.

To the photographic emulsion and the non-photosensitive hydrophilic colloid layer, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N
-Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-
Dihydroxydioxane), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ), Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardeners and the like can be used alone or in combination. These hardeners are RD 176,
17643 (issued in December 1978), pages 26A-C.

Various other additives are used in the light-sensitive material. For example, desensitizers, plasticizers, slip agents, development accelerators, oils and the like can be mentioned.

The support used for the light-sensitive material is transparent,
It may be either non-permeable but is preferably a permeable plastic support. For plastic supports,
What consists of a polyethylene compound (polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (triacetate cellulose, etc.), a polystyrene compound, etc. is used. As the thickness of the support,
Preferably 50 to 250 μm, particularly preferably 70 to 2
00 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after forming the film. The most preferable is after the film formation and after the emulsion coating, but may be after the emulsion coating. The conditions of the heat treatment are preferably 45 ° C. to the glass transition temperature for 1 second to 10 days. From the viewpoint of productivity, it is preferable to set the time within one hour.

Further, it is preferred that the compounds described below are contained in the constituent layers of the light-sensitive material. (1) Solid dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having acid group JP-A No. 62-237445, Compound (8) described on page 11, lower left column, line 11 to page (25), lower right column, line 3 ) Acidic polymer JP-A-6-186659, page (10) [0036]-
(17) Compound described on page [0062] (4) Sensitizing dye JP-A-5-224330, (3) page [0017]-
(13) Compound described on page [0040] JP-A-6-194777, page (11) [0042]-
(22) Compound described on page [0094] JP-A-6-242533, page (2) [0015]-
(8) Compound described on page [0034] JP-A-6-337492, (3) page [0012]-
Compound described on page (34) [0056] JP-A-6-337494, page (4) [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938, (3) page [0011]-
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111] to
(32) Compound described in [0157] (7) Nucleation accelerator JP-A-7-114126, page (32) [0158] to
(36) Compound described on page [0169] (8) Tetrazolium compound JP-A-6-208188, page (8) [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556, (5) page [0028]-
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, compound described in pages (7) to (22) (11) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described in, for example, RD17643 (December, 1978), 1871
6 (November 1979) and 308119 (1989)
Dec. 2012).

In the present invention, the processing is preferably carried out by employing an automatic developing machine having at least four processes of development, fixing, washing (or stabilization) and drying.

In a preferred embodiment of the developing solution used in the present invention, the developing agent represented by the formula (A) is used as the developing agent.

In the compound represented by the general formula (A),
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is particularly preferred.

[0162]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxyl group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The formula (A) or the formula [A-a]
The alkyl group in is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. The amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, and the alkoxyl group is preferably a lower alkyl group. An alkoxyl group is preferable, and a phenyl group or a naphthyl group is preferable as the aryl group. These groups may further have a substituent, and the substituent is preferably a hydroxyl group, a halogen atom, an alkoxyl group, a sulfo group. , A carboxyl group, an amide group, a sulfonamide group and the like.

Specific examples of the compounds represented by formulas (A) and [Aa] are shown below, but the present invention is not limited thereto.

[0166]

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[0167]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof, or compounds derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the present invention, the compound represented by the general formula (A) is mainly used as a developing agent mainly occupying 50% or more by mole of a compound capable of developing silver halide in a developer.
It is preferable to use a compound represented by the formula: This is preferable because the effect of using the compound represented by the general formula (A) as a developing agent is excellently exhibited.

In the present invention, the developing agent represented by the general formula (A) and 3-pyrazolidones (1-phenyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone, 1-phenyl-4 -Ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, etc.), aminophenols (o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
Developing agents such as 2,4-diaminophenol or dihydroxybenzenes substituted with a hydrophilic group (hydroquinone monosulfonate, sodium hydroquinone monosulfonate, potassium 2,5-hydroquinonedisulfonate, dihydroxybenzoic acid, etc.); More preferably, they are used in combination. In particular, a combination of ascorbic acid or a derivative thereof and 3-pyrazolidones, and a combination of ascorbic acid or a derivative thereof, 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

When used in combination, the developing agent of 3-pyrazolidones, aminophenols or dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 to less than 0.2 mol per liter of developer. It is preferably used in an amount.

An alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Is preferred. As the pH buffering agent, a carbonate is preferable, and the amount of the carbonate added is 0.1 mL per liter.
It is preferably from 2 to 1.0 mol, more preferably from 0.3 to 1.0 mol.
It is in the range of 0.6 mole.

When the developing agent represented by the formula (A) is used, it is preferable to contain a sulfite as a preservative. The preferable addition amount is 0.02 to 0.9 mol /
Liter is preferable, and particularly preferably 0.1 to 0.3 mol / liter.

Where necessary, dissolution aids (polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants ,
Antifoaming agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or Its alkali metal salts, nitrilotriacetates, polyphosphates, etc.) and development accelerators (U.S. Pat. No. 2,304,025, JP-B-47-45).
No. 541), a hardening agent (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH 8.
5-10.2.

As the fixing solution, those having a commonly used composition can be used. The pH of the fixing solution is generally 3 to
8 As a fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate;
In addition to thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

A water-soluble aluminum salt (aluminum chloride, aluminum sulfate, potassium alum, etc.) and an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde, etc.) acting as a hardener can be added to the fixing solution.

The fixing solution may optionally contain a preservative (sulfite, bisulfite, etc.), a pH buffer (acetic acid, citric acid, etc.),
Compounds such as a pH adjuster (sulfuric acid, sodium carbonate, etc.) and a chelating agent capable of softening water can be included.

In the present invention, the concentration of ammonium ion in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution, particularly preferably in the range of 0 to 0.05 mol / l.

As a fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

It is preferable that the concentration of acetate ion in the fixing solution is less than 0.33 mol / liter. The type of acetate ion is arbitrary and can be applied to any compound that dissociates acetate ion in the fixing solution, but lithium, potassium, sodium, and ammonium salts of acetic acid and acetate are preferably used, and particularly, sodium salt, ammonium salt, and the like. Salts are preferred.
The acetate ion concentration is more preferably 0.22 mol or less, particularly preferably 0.13 mol or less per liter of the fixing solution, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The fixing solution contains salts such as citric acid, tartaric acid, malic acid and succinic acid, and optical isomers thereof. As the salt, lithium salt, potassium salt, sodium salt, ammonium salt and the like, lithium hydrogen tartrate, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartrate, sodium potassium tartrate and the like may be used. Preferred among these are citric acid, malic acid, succinic acid and salts thereof. Most preferred are malic acid and its salts.

In the present invention, it is preferable to carry out a washing treatment with a washing water containing a purifying agent containing an oxidizing agent and a bactericide.

Preferred oxidizing agents include metal or nonmetal oxides, oxyacids or salts thereof, peroxides, and compounds containing organic acid systems. From the viewpoint of discharging to drainage pipes, the oxyacids include sulfuric acid,
Nitrous acid, nitric acid, hypochlorous acid and the like are preferable, and as the peroxide, hydrogen peroxide solution and fentonic acid are particularly preferable. Most preferred is hydrogen peroxide.

These oxidizing agents are preferably supplied in the form of a concentrated liquid or a solid agent from the viewpoint of physical distribution. As a preferred form, a concentrated solution is preferable, a concentrated solution having an oxidizing agent component of 0.1 to 10 mol / l is preferable, and particularly preferably 0.5 to 2.0 mol / l.

In the present invention, a concentrated liquid or solid agent containing an oxidizing agent is mixed with washing water and supplied. The mixing may be performed before entering the washing tank, or the concentrated liquid or solid agent and the washing water may be directly mixed in the washing tank.

The replenishment timing of the oxidizing agent-containing concentrated liquid or the solid agent and water may be fixed at a constant rate per unit time or may be detected in accordance with the processing amount of the light-sensitive material by detecting the processing amount.

The amount of the oxidizing agent to be added to the washing tank is preferably in the range of 1/2 mol to 10 mol equivalents, and particularly preferably in the range of 1/2 mol to 3 mol equivalents, with respect to the thiosulfate brought into the photosensitive material. It is.

In the water washing of the present invention, in order to make the oxidizing agent act effectively, it is also a preferable embodiment to coexist with a compound such as a preservative or a bactericide.

The bactericide preferably used is not particularly limited as long as it does not adversely affect the photographic performance. Specific examples include thiazolylbenzimidazoles, isothiazolones, and the like.
Chlorophenol type, bromophenol type, thiocyanic acid and isothianoic acid type, acid azide type, diazine and triazine type, thiourea type, alkylguanidine type, quaternary ammonium salt type, organic tin and organic zinc compound type, cyclohexylphenol type, There are various antibacterial agents and fungicides, such as active halogen compounds such as imidazole and benzimidazole, sulfamide, and chlorinated sodium isocyanurate, chelating agents, sulfites, and antibiotics represented by penicillin. In addition, L.I. E. FIG. Wes
t; Water Quality Criteria,
Photo. Sci. and Eng. , Vol9, N
o. 6 (1965): a fungicide described in JP-A-55-111
No. 942, No. 57-8542, No. 57-157244
Nos. 58-105145 and 59-126533
Various fungicides described in No. 3 etc .; "Bactericidal and Fungicide Chemistry" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Bacterial and Fungicide Technical Handbook", Japan Society of Bactericidal and Fungicide, Gihodo (Showa 61) Chemicals and the like as described can be used. Specific examples are shown below, but the present invention is not limited thereto. 1: 5-chloro-2-methyl-4-isothiazoline-3-
On 2: 2- (4-thiazolyl) -benzimidazole 3: methyl isothiocyanate 4: N- (3,5-dichlorophenyl) -N '-(4-
Fluorophenyl) thiourea 5: 4-chloro-3,5-dimethylphenol 6: 2,4,6-trichlorophenol 7: sodium dehydroacetate 8: sulfanilamide 9: 3,4,5-tribromosalicylanilide 10: Potassium sorbate 11: Benzalkonium chloride 12: 1-Bromo-3-chloro-5,5-dimethylhydantoin 13: Monochloroacetamide 14: Monobromoacetamide 15: Monoiodoacetamide 16: Benzimidazole 17: Cyclohexylphenol 18: 2 -Octyl-isothiazolin-3-one 19: ethylenediaminetetraacetic acid 20: nitrilo-N, N, N-trimethinephosphonic acid 21: 1-hydroxyethane-1,1-diphosphonic acid 22: ethylenediamine-N, N, N ' , '-Tetramethylenephosphonic acid 23: chlorinated sodium isocyanurate 24: 2-methyl-4-isothiazolin-3-one 25: 10,10'-oxybisphenoxyarsine 26: 1,2-benzisothiazolin-3-one 27 : Thiosalicylic acid For these exemplified compounds, see US Pat. No. 2,767,
No. 172, No. 2,767,173, No. 2,76
No. 7,174, No. 2,870,015, British Patent No. 848,130, and French Patent No. 1,555,416 describe synthesis methods and examples of application to other fields. I have. Some are commercially available, and Predentol O
N, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600
(The above are manufactured by Permachem Asia Co., Ltd.), Fine Side J-
700 (manufactured by Tokyo Fine Chemical Company) ProzelGX
L (manufactured by ICI Company).

When the above disinfectant is supplied into the washing water, it is preferably 0.01 to 50 g / l, more preferably 0.05 to 20 g / l. When contained as a detergent, 0.1 to 50 g based on the detergent.
/ Liter, more preferably 1 to 20 g / liter.

As the preservative used in the present invention, a compound having a polyalkylene oxide chain represented by the following general formula (PO) is preferable.

Formula (PO) HO (CH ₂ CH ₂ O) _a
[CH (CH ₃ ) CH ₂ O] _b (CH ₂ CH ₂ O) _c H Here, a, b, and c are each a positive integer.

The compound represented by the general formula (PO) is a compound in which propylene glycol is added as a hydrophobic group and ethylene oxide is added as a hydrophilic group. Average molecular weight of 20
00-8500, polypropylene glycol (PPG)
The molecular weight is preferably from 1400 to 2400, and the ethylene oxide (EO) mass% in the total molecule is preferably about 40 to 85%, and particularly preferably, a + c is about 150 and b is about 30 in the general formula.

As such compounds, commercially available products
For example, there are "Pluronic series" nonionic surfactants manufactured by Asahi Denka Co., Ltd., and the following are specifically preferred.

[0196]

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The compound having a polyalkylene oxide chain is added in an amount of 1 to 1000 ppm with respect to washing water.
More preferably, it is 10 to 100 ppm, and when contained as a purifying agent, 0.01 to 10% with respect to the oxidizing agent,
Preferably it is 0.1-5%.

Other preservatives used in the present invention include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline, salicylic acid, quinolinic acid and derivatives thereof, and salts thereof, preferably salicylic acid and salts thereof. And their salts.

The purifying agent according to the present invention preferably contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. The chelate stability constant with calcium is the logarithm of the formation constant when one chelating agent binds to one calcium ion, and 20
It was measured under conditions of ° C and an ionic strength of 0.2.
Specifically, maleic acid, glycolic acid, gluconic acid,
Organic acids such as glucoheptanoic acid, tartaric acid, citric acid, succinic acid, salicylic acid, ascorbic acid, erythorbic acid, glycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as nitrilotriacetic acid and derivatives thereof, and the like. Salt. Gluconic acid and citric acid are preferred as organic acids, and ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are preferred as aminopolycarboxylic acids.

These compounds are used in an amount of about 0.005 to 0.2 mol, preferably 0.005 to 1 mol per liter of washing water.
Used at ~ 0.1 mol.

When the washing time is less than 20 seconds, the effect of the present invention is remarkable, preferably when it was less than 16 seconds, and more preferably when it was less than 12 seconds.

In the present invention, a developing and fixing replenisher prepared from a solid processing agent can be used. The solid processing agent referred to here is a powder processing agent, a tablet, a pill, a granule, or the like,
It has been subjected to moisture proof processing as required. Pastes and slurries are semi-liquid and inferior in storage stability, and have a risk of transportation, and are not included in the solid processing agents referred to in the present invention if they are regulated.

Here, the powder means an aggregate of fine crystals. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. A tablet is obtained by compressing powder or granules into a certain shape.

Among the above solid processing agents, tablets are preferably used because of high replenishment accuracy and easy handling.

In order to solidify the photographic processing agent, a concentrated solution, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is temporarily added to the surface of the photographic processing agent. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Laid-Open Nos. 4-29136 and 4-85).
No. 533, No. 4-85534, No. 4-85535,
4-85536 and 4-172341).

A preferred method for producing a tablet is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet. Simply mixing the solid processing agent components, the solubility and storage stability are improved over the solid processing agent formed by the tableting process,
As a result, there is an advantage that the photographic performance becomes stable.

Granulation methods for tablet formation include rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used.
For tablet formation, the average particle size of the obtained granules is 100 to 800 μm in that the granules are mixed and pressed and compressed, whereby the components become non-uniform, so-called segregation is unlikely to occur. It is preferable to use one, more preferably 200 to
750 μm. Further, the particle size distribution indicates that 60
% Is preferably within a deviation of ± 100 to 150 μm. Next, when pressing and compressing the obtained granules, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a briquetting machine can be used. . The solid processing agent obtained by pressurization and compression can take any shape, but the productivity,
From the viewpoint of handleability and the problem of dust when used on the user side, a cylindrical type, so-called tablet, is preferred.

More preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Furthermore, powder processing agents are described in, for example, JP-A-54-133332, British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861 as described in general methods. Can be manufactured.

The bulk density of the solid processing agent is preferably from 1.0 to 2.5 g / cm ³ in the case of tablets from the viewpoint of its solubility and the effects of the object of the present invention. / C
When the strength is larger than m ³ , the strength of the obtained solid material is 2.5
If it is smaller than g / cm ³ , it is more preferable in view of the solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agent is used at least for the developer and the fixing agent, but can be used for other photographic processing agents such as other rinsing agents. Further, it is the developer and the fixing agent that can exclude the regulation of the liquid dangerous substance. Most preferably, all the processing agents are solidified, but at least the developer and the fixing agent are preferably solidified.

The solid treating agent can be solidified only for a part of a certain treating agent, but it is preferable that all components are solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit.
It is also desirable that the separate components are packaged in the order in which they are periodically charged repeatedly.

When the developer is solidified, it is preferable that all of the alkali agent and the reducing agent are solidified, and in the case of tablets, it is preferable to use at least three agents, most preferably one agent. Also, when the solid processing agent is divided into two or more agents,
It is preferable that the plurality of tablets and granules are packaged in the same manner.

When the fixing agent is solidified, the base agent, preservative, and hardening agent such as aluminum salt are all solidified, and in the case of tablets, at least 3 agents, most preferably 1 agent or 2 agents It is preferable to use an agent. When the solid treatment is performed by dividing into two or more agents, it is preferable that the plurality of tablets and granules are packaged in the same manner. In particular, it is preferable in terms of handling that the aluminum salt be solid.

Examples of the package of the solid processing agent include polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or drawn), polyvinyl chloride,
Polyvinyl acetate, nylon (stretched, unstretched), polyvinylidene chloride, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PE
T), other polyesters, hydrochloride rubber, acrylonitrile-butadiene copolymer, epoxy-phosphate resins (polymers described in JP-A-63-63037, 57-3)
Synthetic polymers and pulp such as the polymer described in No. 2952).

[0216] These are preferably made of a single material. However, when used as a film, the film may be laminated and bonded, or may be used as a coating layer, or may be a single layer. Further, it is more preferable to use various gas barrier films, for example, using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above synthetic resin films.

In order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ²・ 24hr ・ atm or less (20 ℃ ・ 65% RH
), More preferably 30 ml / m ² · 24 hr · at
m or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
m, more preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film or a laminated (polymer) resin film of two or more layers.

When the treating agent is packaged or bound or coated with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, Hydroxypropyl cellulose type,
Film or binder composed of pullulan, dextran or gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline or polyethylene glycol base Agents are preferably used, and among them,
Especially those of polyvinyl alcohol type and pullulan type,
It is more preferably used from the viewpoint of the effect of coating or binding.

The thickness of the water-soluble film is preferably from 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film, and the precipitation of crystals in an automatic developing machine. 80 μm is preferable,
Particularly, those having a thickness of 20 to 60 μm are preferable.

Further, the water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

The tensile strength of the water-soluble film was 4.9 × 1
0 ⁶ ~4.9 × 10 ⁷ Pa, more preferably a preferably ^{9.8 × 10 6 ~2.45 × 10 8} Pa, particularly preferably ^{1.47 × 10 7 ~9.8 × 10 7} Pa It is. These tensile strengths are measured by the method described in JISZ-1521.

Also, photographic processing agents packaged or bound or coated with a water-soluble film or binder can be used during storage, transportation, and handling to prevent atmospheric humidity such as high humidity, rain and fog, and In order to prevent damage from sudden contact with water due to splashing or wet hands, it is preferable that the film is wrapped with a moisture-proof packaging material, and the moisture-proof packaging material is preferably a film having a thickness of 10 to 150 μm. Polyethylene film such as polyethylene terephthalate, polyethylene and polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, etc. Polycarbonate, acrylonitrile and metal foils such as aluminum, metallized poly Preferably at least one selected from over the film, or may be a composite material using the same.

Further, when the moisture-proof packaging material is a degradable plastic,
It is particularly preferable to use a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those composed of natural polymers, microorganism-produced polymers, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. And a group in which a group which is excited by ultraviolet rays and leads to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both the functions of photodegradability and biodegradability at the same time can be used favorably.

The specific representative examples are as follows. Examples of biodegradable plastics include (1) natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. (2) Microbial-produced polymer PHB-PHV (3-hydroxybutyrate and 3 -Bio-Valerate)).
pol ", cellulose produced by microorganisms, etc. (3) Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or copolymers or mixtures thereof (4) Blending of biodegradable natural polymers to plastics Biodegradability Examples of good natural polymers include starch and cellulose, and those having shape disintegration in addition to plastics. Photodegradable plastics include (5) introduction of carbonyl group for photodisintegration, etc. Alternatively, an ultraviolet absorber may be added.

With respect to such degradable plastics,
"Science and Industry", Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July 1990, 23.
~ 34 pages and the like can be used.
Also, Biopol (Biopol: manufactured by ICI), Ec
o (Eco: manufactured by Union Carbide), Eco
lite (Ecolight: Eco Plastic), Ecostar (Ecostar: St. Lawre)
commercially available decomposable plastics such as No. Starch (manufactured by Nippon Unicar) and Knuckle P (manufactured by Nippon Unicar).

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² · 24 hr or less.
It is more preferably 5 g · mm / m ² · 24 hr or less.

The developing solution and the fixing solution are stocked in the replenishing device, and the processing solution is replenished according to the processing amount and the operating time of the automatic developing machine. When the replenisher is a liquid, it may be stocked and replenished inside or outside the replenisher, or may be stocked and replenished in the form of a concentrated solution. When the replenisher is a solid agent, the replenisher can be dissolved in the replenisher, and the replenisher can be stocked and replenished.

[0231] In response to a demand for reducing the amount of waste liquid, the light-sensitive material of the present invention is processed while replenishing a fixed amount in proportion to the area of the light-sensitive material. The replenishment rate of the fixer is 50 per m ²
~ 300 ml. Preferably it is 70-250 ml. If the amount is less than 50 ml, fixing may be insufficient in the case of rapid processing. The developer replenishment rate is 30 to 1 per m ²
It is 50 ml. Preferably it is 50-100 ml.
If it is less than 30 ml, the density of the image may be insufficient in the case of rapid processing. The replenishment amount of the fixing solution and the replenishment amount of the developer referred to herein indicate the replenishment amount. Specifically, it is the replenishment amount of each of the developing mother liquor and the fixing mother liquor when replenishing the same liquor. The total amount of the concentrated solution and water, when replenished with a solution obtained by dissolving the solid developing agent and the solid fixing agent in water, the total amount of the respective solid processing agent volume and the volume of water, When the solid developing agent and the solid fixing agent and water are separately replenished,
It is the total amount of each solid processing agent volume and water volume.

In the case of replenishment with a solid processing agent, it is preferable to represent the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the additional replenishing water. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, respectively.
Different liquid or solid processing agents may be used.

The temperature of the developing, fixing, washing and / or stabilizing baths is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

When processing is performed using an automatic developing machine from the demand for shortening the developing time, it is a preferable embodiment that the film transport speed (line speed) of the automatic developing machine is 1000 mm / min or more. Particularly preferably, 1200 mm /
min or more. Further, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone is preferably 10 to 70 seconds. The total processing time referred to here includes the total processing time required for processing the black-and-white photosensitive material, and specifically, for example, development, fixing, bleaching, washing, stabilizing processing, drying, etc. necessary for processing. Time including all the time of the process, that is, Dr
It is the time of y to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
More preferably, the total processing time (Dry to Dry)
Is 10 to 60 seconds. Also, in order to stably run a large amount of photosensitive material of 100 m ² or more, the effect of the present invention was great when the washing time was less than 20 seconds.

In order to remarkably exert the effects of the present invention, a heat transfer material (60 to 130 ° C.) having a temperature of 60 ° C. or higher is required for the automatic developing machine.
° C heat roller, etc.) or radiant object with 150 ° C or higher (tungsten, carbon, nichrome, zirconium oxide
Heat is emitted by passing a current directly through a mixture of yttrium oxide / thorium oxide, silicon carbide, etc., or heat is transmitted from a resistance heating element to a radiating element such as copper, stainless steel, nickel, or various ceramics to generate heat and generate infrared rays. And those having a drying zone are preferably used.

An automatic developing machine having the following method and mechanism can be preferably used. (1) Deodorizer JP-A-64-37560, upper left column of page (2) to upper left column of page (3) (2) Waste liquid treatment method JP-A-2-64638, lower left column of page (2) to page (5) Lower left column (3) Rinse bath between developing bath and fixing bath JP-A-4-313949 (18), p.
(21) "0065" (4) Water replenishment method JP-A-1-281446, (2) Lower left column to lower right column of page (5) Detecting outside air temperature and humidity to control drying air of automatic developing machine Methods JP-A-1-315745, lower right column of page (2) to lower right column of page (7) and JP-A-2-108051, lower left column of page (2) to lower left column of page (3) (6) Fixing waste liquid Silver recovery method JP-A-6-27623, page (4) "0012"-
(7) Page "0071".

[0237]

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

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and water-soluble halide solution C comprising sodium chloride and potassium bromide
Was added to Solution A at a constant flow rate of pH 3.0 at 46 ° C. at a constant flow rate for 5 minutes, and after 3 minutes, aqueous silver nitrate solution D and water-soluble halide solution E were added at a constant flow rate for 40 minutes. And 0.23 μm silver chlorobromide (AgCl / AgBr =
(65/35 mol%). At this time, the silver potential (EAg) was 120 mV at the end of the mixing. Subsequently, after unnecessary salts were removed by ultrafiltration, 15 g of gelatin was added per mole of silver to adjust the pH to 5.45, and the mixture was dispersed at 55 ° C. for 30 minutes. The silver potential of the obtained emulsion was 200 mV (40 ° C.).

Liquid A Ossein gelatin 49 g Nitric acid (5%) 6.5 ml Ion exchange water 4946 ml Sodium chloride 2.3 g Liquid B Silver nitrate 47.9 g Nitric acid (5%) 7.9 ml Ion exchange water 455 ml Liquid C ion exchange water 500 ml Potassium bromide 13 g Sodium chloride 11.8 g Ossein gelatin 13 g Liquid D Silver nitrate 1150 g Nitric acid (5%) 38 ml Deionized water 1520 ml Liquid E Ossein gelatin 43 g Potassium bromide 311 g Sodium chloride 285 g Na_Three[IrCl₆2.2 mg Na [RhCl_Five(H_TwoO)] 0.33 mg Stabilizer 4-hydroxy per mole of silver was added to the obtained emulsion.
-6-methyl-1,3,3a, 7-tetrazaindene
1 × 10^-3Mol, potassium bromide 8.5 × 10 ^-FourMole,
Stabilizer 1-phenyl-5-mercaptotetrazole
1.5 × 10^-3PH 5.6, EAg12
Adjusted to 3 mV. Sulfur flower dispersed in fine particles
2 × 10 atoms^-Five1.5 × 10 mol and chloroauric acid
^-FiveAfter adding 100 moles and performing chemical ripening at 62 ° C for 100 minutes,
Stabilizer 4-hydroxy-6-methyl-1,3,3a, 7
3 × 10 tetrazaindene^-3Mole was added. 50 ℃
And then sensitizing dye S-1 and sensitizing dye S-2
2 × 10 per mole of silver ^-FourMole was added. like this
The resulting emulsion is referred to as a silver halide emulsion A.

[0240]

Embedded image

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was applied to both sides. And dried at 100 ° C. for 1 minute.
The numerical values indicate the weight per 1 m ² .

(Undercoat layer) 2-hydroxyethyl methacrylate / butyl acrylate / t-butyl acrylate / styrene copolymer (25/30/25/20 mass% ratio) 0.5 g Surfactant A 3.6 mg hexamethylene -1,6-bis (ethylene urea) 10 mg (Antistatic layer) After a corona discharge of 10 W / (m ² · min) was applied to a polyethylene terephthalate support provided with an undercoat layer, an antistatic layer having the following composition was formed on one surface. 70m / min
Apply using a roll-fit coating pan and air knife at a speed of 90 ° C., dry at 90 ° C. for 2 minutes,
Heat treated at 90 ° C. for 90 seconds.

Water-soluble conductive polymer B 0.6 g Hydrophobic polymer particle C 0.4 g Polyethylene oxide compound (Mw = 600) 0.1 g Curing agent E 0.1 g

[0244]

Embedded image

The following first layer (emulsion layer) was formed on one side (on the undercoating layer) of the support, which had been subjected to the above-mentioned subbing process, from the support side so that the coating weight per 1 m ² was as shown below. , Second
The layer (protective layer) was simultaneously coated in multiple layers and cooled and set.

Then, the following backing layer was coated on the opposite antistatic layer at a coating speed of 200 m / min.
After cooling and setting at the same temperature and drying both sides simultaneously, silver halide photographic material samples 101 to 116 were obtained.

First layer (emulsion layer): Coating solution pH 5.2 Gelatin 1.92 g Silver halide emulsion A 3.63 g as silver Amount of hydrazine derivative H-34 Amount shown in Table 1 Hydrazine derivative H-39 Table 1 Amount described Benzyl adenine 0.02 g Colloidal silica / vinyl acetate / vinyl pivalinate suspension polymer (75 / 12.5 / 12.5 mass% ratio) 1.4 g Sodium polystyrene sulfonate (average molecular weight 500,000) 0.015 g Vinyl acetate / vinyl pivalate suspension polymer (1/1% by mass ratio) 1.4 g Compound of general formula [II-1] of the present invention Amount shown in Table 1 Second layer (protective layer) Gelatin 0.90 g Matting agent (monodispersed polymethyl methacrylate having an average particle size of 3 μm) 0.045 g Compounds of the general formulas [I-1] to [I-3] of the present invention. Promoter Na-21 0.01 g fungicides Z 0.005 g lubricant R21 75 mg / m ² hardener Q 0.07 g (backing layer) Gelatin 3.2g dye F-1 0.05 g Dye F-2 0.04 g Dye F-3 0.02 g Suspension polymer of colloidal silica / vinyl acetate / vinyl pivalate (75 / 12.5 / 12.5% by mass ratio) 0.7 g Sodium polystyrene sulfonate 0.010 g Matting agent (average) Monodispersed polymethyl methacrylate having a particle size of 3 μm) 0.045 g Hardener H-1 0.05 g Hardener H-2 0.07 g

[0248]

Embedded image

[0249]

Embedded image

H-1: CH ₂ ＣＨCHSO ₂ CH ₂ CONH
CH ₂ CH ₂ NHCOCH ₂ SO ₂ CH = CH _{2 The} applicability (the occurrence of coating failure) during the preparation of the photosensitive material sample was evaluated as follows. << Applicability >> The applicability of the photosensitive material sample at the time of application was evaluated in five ranks as follows. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use.

1: The coating liquid cannot be applied on the base with a uniform film thickness. 2: When 100,000 m ^{2 is} applied, 10 or more coating defects occur. 3: When 100,000 m ^{2 is} applied, 2 or more, 10 locations. Less than 4 coating defects occurred. 4: One coating defect occurred at 100,000 m ² coating. 5: No coating defects occurred. After applying wedge exposure using these samples, the following processing conditions 1, processing Each development process was performed under the condition 2, and each characteristic was evaluated. (Processing condition 1) (Process) (Temperature) (Time) Current image 35 ° C 30 seconds Fixed 35 ° C 20 seconds Rinse room temperature 20 seconds Squeeze / dry 50 ° C 30 seconds Total 100 seconds (Processing condition 2): Rapid Example of processing (Step) (Temperature) (Time) Current image 38 ° C 15 seconds Fixing 37 ° C 15 seconds Rinse at room temperature 15 seconds Squeeze / dry 50 ° C 15 seconds Total 60 seconds Each treatment liquid formulation is as follows. Developing solution HQ (per liter of working solution) Pure water 224 ml Diethylenetriaminepentaacetic acid / sodium pentasodium 1.0 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g Potassium bromide 4 g Borate 8 g Potassium carbonate 55 g Diethylene glycol 40 g 5-methylbenzotriazole 0 0.21 g 1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone (dimesone S) 0.85 g hydroquinone 20 g potassium hydroxide 18 g It was dissolved according to the formulation to make a total amount of 400 ml. When used, it is mixed with 600 ml of pure water to make 1 liter. The pH of the working solution was adjusted to 10.4. Fixing solution (start solution: per liter of working solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Sodium gluconate 5 g Trisodium citrate dihydrate 12 g Citric acid 12 g Sulfuric acid to make the pH of the working solution 5.4 Adjust to 1
Finished to liters. Fixing solution (replenisher: 2x concentrated solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Sodium gluconate 5 g Trisodium citrate dihydrate 12 g Citric acid 12 g Sulfuric acid to make the pH of the working solution 5.2 Adjust to 5
Finished to 00 ml. Rinse water A solution obtained by adding 8.8 ml of the following purifying agent to 1 liter of tap water was placed in a rinsing tank to obtain rinsing water. (Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35% by mass hydrogen peroxide water 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g Diethylenetriaminepentaacetic acid / 5 sodium 10 g Finished to 1 liter with pure water. (Blackening ratio of photosensitive material) The blackening ratio of the photosensitive material was adjusted to 8%. (Amount of replenishment of processing solution) The developing and fixing replenisher, the purifying agent and the tap water for dilution of the above formula are directly replenished to the developing tank, the fixing tank and the washing tank, respectively, under the following replenishing amount conditions 1 and 2 respectively. did. The following evaluation was performed using each developed sample. << Adhesion of Stain >> The developing solution, fixing solution and washing water prepared by the above-mentioned prescription were filled in an automatic developing machine LD-T1060 (manufactured by Dainippon Screen Mfg. Co., Ltd.). In this state, each light-sensitive material was processed at a rate of 30 m ² per day with two kinds of replenishment amounts of the replenishment amount conditions 1 and 2 and running was performed for one week. Two days after the end of the running, the rank of the adhesion of dirt was evaluated based on the degree of dirt (silver sludge) of the processed film obtained by processing each photosensitive material. 1 to the order of dirt adhesion
The ranking is made in five steps of 5, and rank 5 is a state in which no dirt is attached. Rank 3 is a level that can withstand practical use, and ranks 1 and 2 are levels that are not practically preferable. << Sensitivity >> The photosensitive material sample was subjected to wedge exposure using a semiconductor laser of 633 nm, and the processing solution and the automatic developing machine LD-T1060 (described above), the developing solution, the fixing solution, the washing water and the oxidizing agent-containing purifying agent were used. Developing treatment was performed under the above-mentioned conditions to obtain the sensitivity. At this time, the sensitivity of the sample 101 was set to 100
As relative values.

The above progress is shown in Table 1, and the results are shown in Tables 2 and 3.

[0253]

[Table 1]

[0254]

[Table 2]

[0255]

[Table 3]

As is clear from the table, the light-sensitive material of the present invention (the constitution of the first or second aspect of the present invention) adheres dirt (the light-sensitive material) while maintaining the sensitivity by adding the compound of the present invention. It can be seen that the adhesion of dirt does not deteriorate even when a large number of sheets are processed with low replenishment in the processing (the structure of the invention according to claim 3 or 4).

Example 2 The sample prepared in Example 1 was exposed and processed under the following processing conditions in the same manner as in Example 1. The items and methods for each evaluation were the same as in Example 1. (Processing conditions) Using a developing solution and a fixing solution having the following compositions, an automatic developing machine GR-26 was used to adjust the specific surface area of the developing tank to 8 cm ² /
L (definition of specific surface area: description of paragraph 0085 of JP-A-7-77782), and rapid treatment was performed under the following conditions. After dissolving the tablets with a dissolving mixer, the developing and fixing were finished to make 1 L for 25 tablets. <Processing liquid formulation> (1) Replenished developing tablet (D-SR) Preparation of granulated A parts (per liter of liquid used) Diethylenetriamine pentaacetic acid / 5 sodium salt 1.00 g Sulfite 0.25 mol 8-mercaptoadenine 0 0.06 g 5-methylbenzotriazole 0.27 g Potassium bromide 4.72 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (A-1) 35.6 g Isoelite P (Salt water port refined sugar) 20 g D-mannitol (Kao Corporation) 4 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated for 10 minutes at room temperature with a commercially available stirring granulator.
The granulated product was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated product A part.

Production of granulated B part (per liter of liquid used) Carbonate 1.0 mol D-mannitol (Kao Corporation) 5 g Lithium hydroxide 3.4 g The above materials were mixed in a commercially available bantam mill for 30 minutes. After granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer, and the granulated product B
Got the parts.

The mixture obtained by thoroughly mixing the above-mentioned parts A and B for 10 minutes was mixed with the machine UDINA DFE 30/4.
9. Using a 0 tableting machine (manufactured by Masina Co., Ltd.)
Filling with 83 g, 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² . (2) Supplementary fixing tablet Preparation of granulated A parts (for 1 L of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P (Salt Water Port Refining Co., Ltd.) 5 g Pine flow (trade name: Matsutani Chemical) 8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. At 40 ° C for 2 hours
Got the parts.

Production of granulated B parts (per liter of liquid used) Boric acid 10 g Tartaric acid 3 g Sodium hydrogen sulfate 18 g Aluminum sulfate / 18 hydrate 37 g Pine flow (trade name: Matsutani Chemical) 4 g After mixing at room temperature for 10 minutes at room temperature with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to obtain granulated product B.
Got the parts.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was used in a Masina UD / DFE30 /
25 tablets with a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² using a 40 tableting machine at a filling amount of 11.0 g per tablet.

Tables 4 and 5 below show the obtained results.

[0263]

[Table 4]

[0264]

[Table 5]

As is clear from the table, the effect of the present invention can be obtained even when a solid processing agent is used, or when a rapid processing is performed using a solid processing agent (the structure of the invention of claim 5 of the present invention). But it turns out to be excellent.

Example 3 The sample prepared in Example 1 was exposed in the same manner as in Example 1, and processed in the same manner as in Example 1 except that the developing solution was changed to an AQ developing solution having the following formulation.

Example 1 for each evaluation item and method
The same was done. AQ developer Diethylenetriaminepentaacetic acid / 5 sodium 1 g Sodium sulfite 30 g Potassium carbonate 53 g Potassium hydrogen carbonate 17 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 40 g 1- Phenyl-5-mercaptotetrazole 0.025 g Potassium bromide 4 g 5-Methylbenzotriazole 0.21 g 2,5-Dihydroxybenzoic acid 5 g 8-Mercaptoadenine 0.07 g Potassium hydroxide was added to adjust the pH to 9.8. Finished to liters.

Tables 6 and 7 show the results.

[0269]

[Table 6]

[0270]

[Table 7]

From the table, it can be seen that the effects of the present invention are also effective when a developer containing an ascorbic acid derivative is used instead of hydroquinone (the constitution of the sixth aspect of the present invention).

As demonstrated in the above examples, according to the present invention, high sensitivity, excellent coating properties, and little adhesion of silver sludge, and when the photosensitive material is processed in large quantities with low replenishment, or when processed rapidly However, it is possible to provide a silver halide photographic light-sensitive material which is hardly stained with silver of the light-sensitive material, particularly a silver halide photographic light-sensitive material for an image setter and a processing method therefor. This is particularly effective when processing a photosensitive material that has been spectrally sensitized to 600 to 800 nm. The present invention is also effective when the developer contains an ascorbic acid derivative.

[0273]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material for printing plate making which hardly causes silver stain on the light-sensitive material at the time of development processing and a processing method thereof. Further, even when the photosensitive material is processed in a large amount with low replenishment or when the photosensitive material is rapidly processed, a silver halide photographic light-sensitive material for printing plate making, which is hardly stained with silver of the photosensitive material, and a processing method thereof can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03C 5/26 G03C 5/26 520 520 5/30 5/30 5/31 5/31 5/395 5 / 395

Claims (6)

[Claims] 1. A support having at least one light-sensitive silver halide emulsion layer on one side of a support, having the following general formula [I-
1) a silver halide photographic light-sensitive material containing a compound represented by the formula [I-2] or [I-3], and further containing a compound represented by the following formula [II-1]: material. Formula [I-1] _{Rf- (L 1) m - (} Y 1) in _n -X (wherein, Rf represents an aliphatic group containing at least one fluorine atom, L ₁ is a divalent linking group Wherein Y ₁ represents an alkylene oxide group or an alkylene group which may have a substituent, X represents a hydrogen atom, a hydroxyl group, an anionic group or a cationic group, and m represents 0 or 1 to 5
And n represents 0 or an integer of 1 to 40. ) General formula (I-2) _{Rf- (O-Rf ') n1} -L 2 -X' m1 ( wherein, Rf represents an aliphatic group containing at least one fluorine atom, Rf 'is at least one It represents a fluorine atom-containing alkylene group, L ₂ represents a simple bond or a linking group, X ′ represents a hydroxyl group, an anionic group or a cationic group, and n1 and m1 each represent an integer of 1 or more. ) formula [I-3] _{[(Rf "O) n2 - (} PFC) -CO-Y 2 ] _k -L ₃ -
X _{"m @ 2} (wherein, Rf" represents a perfluoroalkyl group containing 1 to 4 carbon atoms, (PFC) represents a perfluorocycloalkylene group, Y ₂ is a linking group containing an oxygen atom or a nitrogen atom L ₃ represents a mere bond or a linking group; X ″ represents a water-solubilizing polar group containing an anionic group, a cationic group, a nonionic group, or an amphoteric group;
n2 represents an integer of 1 to 5, k represents an integer of 1 to 3,
m2 represents an integer of 1 to 5. ) (In the formula, Z represents a heterocyclic ring containing a nitrogen atom, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a substituted or unsubstituted ammonium cation.) 2. The silver halide photographic light-sensitive material according to claim 1, which contains a hydrazine derivative as a high contrast agent. 3. The processing of the silver halide photographic light-sensitive material according to claim 1 or 2, wherein the replenishment amount of the developer is 30 to 150 ml per m ^{2 of the} photographic material, and the replenishment amount of the fixer is 1 m ^{2 of the} photographic material. A processing method for a silver halide photographic light-sensitive material, wherein the processing is carried out at a rate of 50 to 300 ml. 4. The processing time of the photosensitive material (Dry to
4. The method according to claim 3, wherein (Dry) is 10 seconds to 60 seconds. 5. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the processing is performed using a processing solution prepared from a solid processing agent. 6. The processing method for a silver halide photographic material according to claim 3, wherein the processing is performed with a developer containing a developing agent represented by the following general formula (A). Embedded image (Each wherein, R ₁ and R ₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a .R ₁ representing a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group R ₂ may combine with each other to form a ring, k
Represents 0 or 1, and when k = 1, X represents -CO- or -C
M ₁ and M ₂ each representing S— each represent a hydrogen atom or an alkali metal atom. )