JP2002323728A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material by which the occurrence of unevenness in density causing a fatal mistake in diagnosis and defects in density due to the sticking of silver sludge and crystals is suppressed under severe processing conditions, e.g. reduced replenishment of a processing solution, prolonged continuous processing or fatigue or concentration of a processing solution when a silver halide photographic sensitive material is processed with an automatic processing machine. SOLUTION: In the processing method in which a silver halide photographic sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloidal layer on the base is processed with an automatic processing machine having at least a developing solution, a fixing solution and washing water, the sensitive material contains a compound of the formula Rf-(O-Rf')n -L1 -Xm or [(Rf"O)n1 -(PFC)-CO-Y1 ]k -L2 -X'm1 and the developing solution contains reductones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to a method suitable for processing a silver halide photographic light-sensitive material with an automatic processor even under severe processing conditions. The present invention relates to a method for processing a photographic material.

[0002]

2. Description of the Related Art Among silver halide photographic materials, X-ray films for medical use include direct medical use, indirect use, CRT use, laser image use, and the like. Have been done. Each medical facility performs processing by an automatic developing machine under various use conditions. From large-scale processing of processing 400 to 500 sheets per day by a large-scale facility to 10-minute processing by a small-scale facility such as a medical practitioner.
There are various types of processing, such as small-scale processing of less than one sheet, and all-day operation of an automatic processor by an emergency hospital for 24 hours / day.

[0003] Since the processing conditions of the automatic developing machine differ from facility to facility, concentration of the processing solution proceeds, and crystals of the processing solution components are formed, and the performance (sensitometry) of the processing film is increased. ) Greatly fluctuates, and in some cases, causes a failure (attachment of a crystal to a film, peeling of a film, etc.). Usually, the solution is renewed once every three months, and once a month, the processing tanks of the automatic developing machine (developing tank, fixing tank, washing tank) and the developing processing racks (developing conveyance rack, fixing conveyance rack, development-fixing water rack, It is recommended to clean (fixing-washing water rack, washing rack, squeeze rack), but even if these processes are performed, the processing stability (performance, failure) may be insufficient. There has been a demand for a processing method using a developing machine.

In particular, it is desired to prevent the occurrence of density unevenness which is likely to occur under severe processing conditions in which the processing solution is concentrated and continuous processing is continued and which is fatal in diagnosis, and density defects due to silver sludge and crystal adhesion. It had been.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to reduce the replenishment of a processing solution when processing a silver halide photographic light-sensitive material with an automatic developing machine. A silver halide photograph with improved density non-uniformity, which is likely to occur under severe processing conditions such as prolonged processing and concentration of processing solution fatigue, which is fatal for diagnosis, and density defects due to silver sludge and crystal adhesion are improved. An object of the present invention is to provide a method for processing a photosensitive material.

[0006]

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

[0007] 1. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. A method for processing a silver halide photographic light-sensitive material, characterized in that the light-sensitive material contains the compound represented by the general formula (1) or (2) and the developer contains reductones.

[0008] 2. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. Processing of a silver halide photographic light-sensitive material, characterized in that the light-sensitive material contains a compound represented by the above general formula (1) or (2), and the developing solution and the fixing solution contain substantially no ammonium salt. Method.

3. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. The photosensitive material contains the compound represented by the general formula (1) or (2), the developer does not substantially contain a glutaraldehyde compound, and the fixer does not substantially contain aluminum ions. A method for processing a silver halide photographic light-sensitive material, comprising:

[0010] 4. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. Processing of a silver halide photographic light-sensitive material, characterized in that the light-sensitive material contains a compound represented by the above general formula (1) or (2), and the developer and the fixer contain substantially no boron compound. Method.

5. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. The light-sensitive material contains the compound represented by the above general formula (1) or (2), and the fixer contains substantially no acetate and contains 0.5 to 1.5 mol / L of sulfite. A method for processing a silver halide photographic material.

6. In a processing method, a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. The photosensitive material contains the compound represented by the formula (1) or (2), and the swelling degree of the photosensitive material during processing with a developing solution and processing with a fixing solution is 100 to 200%. A method for processing a silver halide photographic material.

7. 7. The method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 6, wherein the developer and the fixer are respectively a solid developer and a solid fixer dissolved therein.

Hereinafter, the present invention will be described in detail. The compounds represented by the general formulas (1) and (2) of the present invention will be described.

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

Rf 'represents an alkylene group containing at least one fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms,
Particularly preferred is 2 or 3.

L ₁ represents a simple bond or a linking group, and the linking group is preferably an alkylene group, an arylene group, a divalent linking group containing a hetero atom, or the like.

X represents a hydroxyl group, an anionic group or a cationic group. The anionic group is preferably a carboxyl group, a sulfonic acid group or a phosphoric acid group, and the counter cation is an alkali ion such as a sodium ion or a potassium ion. Metal ions and ammonium ions are preferred. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like.

N and m each represent an integer of 1 or more, and it is preferable that n is 1 or more and 10 or less, and m is 1 or more and 3 or less.

In the general formula (2), Rf ″ represents a perfluoroalkyl group having 1 to 4 carbon atoms,
As the perfluoroalkyl group, a trifluoromethyl group is particularly preferred.

(PFC) represents a perfluorocycloalkylene group, which includes a perfluorocyclooctylene group, a perfluorocycloheptylene group, a perfluorocyclohexylene group, and a perfluorocycloalkylene group. A pentylene group and the like are mentioned, and a perfluorocyclohexylene group is particularly preferred.

Y ₁ represents a linking group containing an oxygen atom or a nitrogen atom, and the linking groups include —OCH ₂ — and —N
HCH ₂ — and the like are particularly preferred.

L ₂ represents a simple bond or a linking group, wherein the linking group is a substituted or unsubstituted alkylene group (eg, ethylene group, propylene group, iso-butylene group, etc.), an arylene group (eg, phenylene group) Group), a combination of an alkylene group and an arylene group (eg, a xylylene group), an oxydialkylene group (eg, —CH ₂ CH ₂₎
OCH ₂ CH ₂ — groups, etc.), thiodialkylenes (eg, —
CH ₂ CH ₂ SCH ₂ CH ₂ — group) and the like, and generally a divalent linking group.

X ′ represents a water-solubilizing polar group containing an anionic group, a cationic group, a nonionic group or an amphoteric group.
Examples of the anionic _{group, -CO 2 H, -CO 2 M} , -SO
_{3 H, -SO 3 M, -OSO} 3 H, -OSO 3 M, - (OC
_{H 2 CH 2) OSO 3 M} , -OPO (OH) 2, -OPO
(OM) ₂ (where M represents a metal ion such as sodium, potassium, calcium or the like or an ammonium ion)
Among them, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are preferable, and as the counter cation, an alkali metal ion such as a sodium ion and a potassium ion, and an ammonium ion are preferable. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like. As the nonionic group, a hydroxyl group is preferable.

N1 represents an integer of 1 to 5, k represents an integer of 1 to 3, and m1 represents an integer of 1 to 5, wherein n1 is preferably 3, and k is preferably 1 or 2, m
It is preferable that 1 is 1.

Hereinafter, specific examples of the compounds represented by the general formulas (1) and (2) of the present invention are shown, but the present invention is not limited thereto.

Compound represented by general formula (1) 1-1. C_FiveF₁₁− (O-CF_Two) -O-PO (ONa)
_Two 1-2. HC₆F₁₂− (O-CF_Two) -O-PO (ON
a)_Two 1-3. C₈F₁₇− (O-CF_Two) -O-PO (ONa)
_Two 1-4. C_TenF_{twenty one}− (O-CF_Two) -O-PO (ON
a)_Two 1-5. C₁₂F_{twenty five}− (O-CF_Two) -O-PO (ON
a)_Two 1-6. C_ThreeF₇− (OC_TwoF_Four) -O-PO (ONa)
_Two 1-7. C_FourF₉− (OC_TwoF_Four) -O-PO (ONa)
_Two 1-8. C_FiveF₁₁− (OC_TwoF_Four) -O-PO (ON
a)_Two 1-9. HC₆F_12-(OC_TwoF_Four) -O-PO (ON
a)_Two 1-10. C₇F_Fifteen− (OC_TwoF_Four) -O-PO (ON
a)_Two 1-11. C₉F₁₉− (OC_TwoF_Four) -O-PO (ON
a)_Two 1-12. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-PO (ON
a)_Two 1-13. C_ThreeF₇− (O-CF_Two)₆-O-PO (ON
a)_Two 1-14. C_FourF₉− (O-CF_Two)₆-O-PO (ON
a)_Two 1-15. C_FiveF₁₁− (O-CF_Two)_Five-O-PO (ON
a)_Two 1-16. HC₆F₁₂− (O-CF_Two)_Three-O-PO (O
Na)_Two 1-17. C_ThreeF₇-[O- (CF_Two)_Three] -COONa 1-18. C_FourF₉-[O- (CF_Two)_Three] -COONa 1-19. C_FiveF₁₁-[O- (CF_Two)_Three] -COONa 1-20. HC₇F₁₄-[O- (CF_Two)_Three] -O-CH
(COONa)_Two 1-21. C₈F₁₇-[O- (CF_Two)_Three] -O-CH
(COONa)_Two 1-22. C_ThreeF₇-[O- (CF_Two)_Five] -COONa 1-23. C_FourF₉-[O- (CF_Two)_Five] -COONa 1-24. C_FiveF₁₁-[O- (CF_Two)_Five] -COONa 1-25. C₇F₁₅-[O- (CF_Two)_Five] -COONa 1-26. C_ThreeF₇− (OC_TwoF_Four)_Five-COONa 1-27. C_FourF₉− (OC_TwoF_Four)_Two-COONa 1-28. C_FiveF₁₁− (OC_TwoF_Four)_Two-COONa 1-29. HC₇F₁₄− (OC_TwoF_Four)_Two-COONa 1-30. C₉F₁₉− (OC_TwoF_Four)_Two-COONa 1-31. C_TwoF_Five− (OC_TwoF_Four)_Three-COONa 1-32. C_TwoF_Five− (OC_TwoF_Four)_Five-COONa 1-33. C_ThreeF₇− (OC_TwoF_Four)_Four-COONa 1-34. C_FourF₉− (OC_TwoF_Four)_Three-COONa 1-35. C_FiveF₁₁− (OC_TwoF_Four)_Three-NHCOCH
(COONa)_Two 1-36. HC₆F₁₂− (OC_TwoF_Four)_Three-NHCOCH
(COONa)_Two 1-37. C_FourF₉− (OC_TwoF_Four)_Two-OCF_TwoCOON
a 1-38. C_FiveF₁₁− (OC_TwoF_Four)_Two-OCF_TwoCOO
Na 1-39. C₇F₁₅− (OC_TwoF_Four)_Two-OCF_TwoCOO
Na 1-40. C_FourF₉-OCF_Two-[O- (CF_Two)_Five] -C
OOK 1-41. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five] -C
OOK 1-42. HC₆F₁₂-OCF_Two-[O- (CF_Two)_Five]-
COOK 1-43. C_FourF₉− (OC_TwoF_Four)_Five-[O- (CF_Two)
_Three] -COOK 1-44. C_FiveF₁₁− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK 1-45. C₆F₁₃− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -COOK 1-46. C₁₂F_{twenty five}− (O-CF_Two) -O-SO_ThreeNa 1-47. C₇F_Fifteen− (OC_TwoF_Four) -OC_ThreeH₆-SO_Three
Na 1-48. C_FourF₉− (O-CF_Two)₆-O-SO_ThreeNa 1-49. HC_FiveF_Ten− (O-CF_Two)_Five-OC_ThreeH₆-S
O_ThreeNa 1-50. HC₆F₁₂− (O-CF_Two)_Three-O-SO_ThreeNa 1-51. C_FiveF₁₁− (OC_TwoF_Four)_Two-OC_ThreeH₆-SO
_ThreeNa 1-52. C₇F_Fifteen− (OC_TwoF_Four)_Two-O-SO_ThreeNa 1-53. C_ThreeF₇− (OC_TwoF_Four)_Four-OC_ThreeH₆-SO_Three
Na 1-54. C_FourF₉− (OC_TwoF_Four)_Three-O-SO_ThreeNa 1-55. HC_FiveF_Ten− (OC_TwoF_Four)_Three-OC_ThreeH₆-S
O_ThreeNa 1-56. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five] -O
-SO_ThreeNa 1-57. C_FourF₉− (OC_TwoF_Four)_Two-[O- (CF_Two)
_Three] -O-SO_ThreeNa 1-58. (HCF_Two)_ThreeC- (OC_TwoF_Four)_Three-OS
O_ThreeNa 1-59. (CF_Three)_TwoCFCF_TwoCF_Two− (O-CF_Two)_Five
-OC_ThreeH₆-SO_ThreeNa 1-60. C₁₁F_{twenty three}− (OC_TwoF_Four) -O-SO_ThreeNa 1-61. C_FourF₉− (OC_TwoF_Four)_Three-NHCO- (C
H_Two)_Three-N⁺(CH_Three)_Three, Br^- 1-62. C_FiveF₁₁− (OC_TwoF_Four)_Two-NHCO- (C
H_Two)_Three-N⁺(CH_Three) _Three, Br^- 1-63. HC₆F₁₂− (OC_TwoF_Four)_Two-NHCO-
(CH_Two)_Three-N⁺(CH_Three)_Three, Br^- 1-64. C_FourF₉− (OC_TwoF_Four)_Three-O-CH_Two-N⁺
(CH_Three)_Two(C_TwoH_FourOH), Br^- 1-65. C_FiveF₁₁− (OC_TwoF_Four)_Two-O-CH_Two-N⁺
(CH_Three)_Two(C_TwoH_FourOH), Br^- 1-66. HC₆F₁₂− (OC_TwoF_Four)_Two-O-CH_Two−
N⁺(CH_Three)_Two(C_TwoH_FourOH), Br^- 1-67. C_FiveF₁₁-OCF_Two− (OC_TwoF_Four) -NHC
O- (CH_Two)_Three-N⁺(CH_Three)_Three, Br^- 1-68. (CF_Three)_ThreeC- (OC_TwoF_Four)_Three-O-CH_Two
-N⁺(CH_Three)_Two(C_TwoH_FourOH), Br^- 1-69. C₁₂F_{twenty five}− (O-CF_Two) -OH 1-70. C₇F₁₅− (OC_TwoF_Four) -OH 1-71. C_FourF₉− (O-CF_Two)₆ -OC_ThreeH₆-OH 1-72. C_FiveF₁₁− (O-CF_Two)_Five-OC_ThreeH₆-OH 1-73. HC₆F₁₂− (O-CF_Two)_Three-OH 1-74. C_FiveF₁₁− (OC_TwoF_Four)_Two-OC_ThreeH₆-OH 1-75. C₇F₁₅− (OC_TwoF_Four)_Two-OC_ThreeH₆-OH 1-76. C_ThreeF₇− (OC_TwoF_Four)_Four-OC_ThreeH₆-OH 1-77. HC_FourF₈− (OC_TwoF_Four)_Three-OC (C_TwoH
_FourOH)_Three 1-78. C_FiveF₁₁− (OC_TwoF_Four)_Three-OC_ThreeH₆-OH 1-79. C_FiveF₁₁-OCF_Two-[O- (CF_Two)_Five] -O
H1-80. C_FourF₉− (OC_TwoF_Four)_Two-[O- (C
F_Two)_Three] -OH 1-81. (CF_Three)_ThreeC- (OC_TwoF_Four)_Three-OH 1-82. (HCF_Two)_TwoCFCF_TwoCF_Two− (OC
F_Two)_Five-OH 1-83. C₁₁F_{twenty three}− (OC_TwoF_Four)_FourOH About the method of synthesizing the compound represented by the general formula (1)
Is the Japanese translation of Tokuhyo Hei 10-500950 and 11-50436
0 can be referred to. Represented by the general formula (2)
Compound 2-1. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆N⁺
(CH_Three)_TwoC_TwoH_FourCOO^- 2-2. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆N⁺
(CH_Three)_TwoC_TwoH_FourSO_Three ^- 2-3. (CF_ThreeO) (PFC) -CONHC_ThreeH₆N
⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- 2-4. (CF_ThreeO)_Three(PFC) -CON (C_ThreeH₆SO
_Three−) C_ThreeH₆N⁺(CH _Three)_TwoH 2-5. (CF_ThreeO) (PFC) -CON (C_ThreeH₆SO_Three
−) C_ThreeH₆N⁺(CH_Three)_TwoH 2-6. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_TwoC
H-CONHC_ThreeH₆N ⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- 2-7. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_TwoC
H-CONHC_ThreeH₆N ⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- 2-8. [(CF_ThreeO) (PFC) -COOCH_Two]_TwoC
H-CONHC_ThreeH₆N⁺(CH_Three)_TwoC_TwoH_FourSO_Three ^- 2-9. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆N⁺
(CH_Three)_TwoC_TwoH_FourOH, Cl^- 2-10. (CF_ThreeO)_Two(PFC) -CONHC_ThreeH₆N
⁺(CH_Three)_TwoC_TwoH_FourOH, Cl^- 2-11. (CF_ThreeO) (PFC) -CONHC_ThreeH₆N⁺
(CH_Three)_TwoC_TwoH_FourOH, Cl^- 2-12. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆N
⁺(CH_Three)_TwoH, Cl^- 2-13. (CF_ThreeO)_Two(PFC) -CONHC_ThreeH₆N
⁺(CH_Three)_TwoH, Cl^- 2-14. (CF_ThreeO) (PFC) -CONHC_ThreeH₆N⁺
(CH_Three)_TwoH, Cl^- 2-15. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
C (CH_Three) N⁺(CH _Three)_TwoH, Cl^- 2-16. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
C (CH_Three) N⁺(CH _Three)_TwoH, Cl^- 2-17. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
C (CH_Three) N⁺(CH_Three)_TwoH, Cl^- 2-18. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
CHC_ThreeH₆N⁺(CH_Three)_TwoH, Cl^- 2-19. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
CHC_ThreeH₆N⁺(CH_Three)_TwoH, Cl^- 2-20. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
CHC_ThreeH6N⁺(CH_Three)_TwoH, Cl^- 2-21. (CF_ThreeO)_Three(PFC) -COO (C_TwoH
_FourO)₁₂H 2-22. (CF_ThreeO)_Two(PFC) -COO (C_TwoH
_FourO)₁₂H 2-23. (CF_ThreeO) (PFC) -COO (C_TwoH
_FourO)₁₂H 2-24. (CF_ThreeO)_Three(PFC) -COO (C_TwoH
_FourO)₁₅CH_Three 2-25. (CF_ThreeO)_Two(PFC) -COO (C_TwoH
_FourO)₁₅CH_Three 2-26. (CF_ThreeO) (PFC) -COO (C_TwoH
_FourO)₁₅CH_Three 2-27. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
CHC_ThreeH₆OH 2-28. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
CHC_ThreeH₆OH 2-29. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
CHC_ThreeH₆OH 2-30. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆C
OONa 2-31. (CF_ThreeO)_Two(PFC) -CONHC_ThreeH₆C
OONa 2-32. (CF_ThreeO) (PFC) -CONHC_ThreeH₆C
OOK 2-33. (CF_ThreeO)_Three(PFC) -CONHC_ThreeH₆S
O_ThreeNa 2-34. (CF^ThreeO)^Two(PFC) -CONHC^ThreeH⁶S
O^ThreeNa 2-35. (CF_ThreeO) (PFC) -CONHC_ThreeH₆S
O_ThreeK 2-36. (CF_ThreeO)_Three(PFC) -CON (C_ThreeH₆S
O_ThreeNa) C_ThreeH₇ 2-37. (CF_ThreeO)_Two(PFC) -CON (C_ThreeH₆S
O_ThreeNa) C_ThreeH₇ 2-38. (CF_ThreeO) (PFC) -CON (C_ThreeH₆S
O_ThreeNa) C_ThreeH₇ 2-39. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
C (CH_Three) COONa 2-40. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
C (CH_Three) COONa 2-41. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
C (CH_Three) COONa 2-42. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
C (COONa)_Two 2-43. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
C (COONa)_Two 2-44. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
C (COONa)_Two 2-45. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
C (CH_Three) SO_ThreeNa 2-46. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
C (CH_Three) SO_ThreeNa 2-47. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
C (CH_Three) SO_ThreeNa 2-48. [(CF_ThreeO)_Three(PFC) -COOCH_Two]_Two
CHC_ThreeH₆SO_ThreeNa 2-49. [(CF_ThreeO)_Two(PFC) -COOCH_Two]_Two
CHC_ThreeH₆SO_ThreeNa 2-50. [(CF_ThreeO) (PFC) -COOCH_Two]_Two
CHC_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)_ThreeFor 3,4
5th place, (CF_ThreeO) In the case of 2, it is the third and fourth place,
(CF_ThreeIn the case of O), it is the fourth place.

For the method of synthesizing the compound represented by the general formula (2), see JP-A-10-158218,
000-505803 can be referred to.

As the reductones according to the first aspect of the present invention, compounds represented by the following general formula (3) are preferably used.

Although the reductones of the present invention may be used for applications such as antioxidants, they are preferably used as a developing agent, so that the effects of the present invention can be further enhanced.

[0031]

Embedded image

In the general formula (3), R ₆ and R ₇ each include those substituted with a hydroxyl group, an amino group (an ethyl group, a butyl group, a hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, etc.). ), An acylamino group (acetylamino, benzoylamino, etc.), an alkylsulfonylamino group (methanesulfonylamino, etc.), an arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), an alkoxycarbonylamino group (methoxycarbonylamino, etc.) ), A mercapto group or an alkylthio group (methylthio, ethylthio, etc.).

Preferred examples of R ₆ and R ₇ include a hydroxyl group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

X is a group of atoms necessary to form a 5- to 6-membered ring, and is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and two vinyl carbon atoms substituted by R ₆ and R ₇ And a carbonyl carbon atom to form a 5- to 6-membered ring.

Specific examples of X include -O-, -C
_{(R 8) (R 9)} -, - C (R 10) =, - C (= O) -,
—N (R ₁₁ ) — and —N =. Here, each of R ₈ , R ₉ , R ₁₀ and R ₁₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxyl group, a carboxyl group, a sulfo group, or the like is given as a substituent). , A hydroxyl group or a carboxyl group. Further, the 5- or 6-membered ring may form a saturated or unsaturated condensed ring.

Examples of the 5- or 6-membered ring include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone,
Each ring includes pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil and the like. Preferred 5
The 6-membered ring includes dihydrofuranone, cyclopentenone, cyclohexanone, pyrazolinone, azacyclohexenone,
Each ring of uracil.

The compound represented by the general formula (3) may form a salt of lithium, sodium, potassium, ammonium and the like.

Specific examples of the reductone represented by the general formula (3) are shown below, but it should not be construed that the invention is limited thereto.

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

Preferred among the above specific examples is ascorbic acid or erythorbic acid (stereoisomer) (3-1). The amount of the above-mentioned reductones may be in the range of 1 to 100 g, preferably 5 to 50 g per liter of developer.

In the present invention, it is preferable from the viewpoint of toxicology that the developer contains substantially no dihydroxybenzene compound. To be substantially free of a dihydroxybenzene compound means that its content is less than 0.001 mol / L.

The fact that the developer and the fixer according to the second aspect of the present invention do not substantially contain an ammonium salt means that the content of the ammonium salt is less than 0.001 mol / L. Preferably, it is not contained at all. Examples of the ammonium salt used in the developer include a development accelerator, and examples of the ammonium salt used in the fixer include ammonium thiosulfate used as a fixing agent.

The fact that the developer according to the third aspect of the present invention does not substantially contain a glutaraldehyde compound means that the content is less than 0.005 mol / L, and that the developer does not contain any at all for the effect of the present invention. Preferably not. Glutaraldehyde takes various forms in the developer, such as glutaraldehyde itself, a monoadduct in which one of two aldehyde moieties is added with one sulfite, a diadduct in which both are added, and a dehydrated condensate. Collectively refers to these compounds as glutaraldehyde compounds,
Content refers to the total amount.

Further, the term "fixer does not substantially contain aluminum ions" means that the content is 0.0001 mol.
/ L, and preferably do not contain any at all for the effects of the present invention. Aluminum ions take various forms in the fixing solution, such as several kinds of hydroxide complexes, acetate complexes, citric acid, and complexes of chelating agents such as tartaric acid. In the present invention, these are all collectively referred to as aluminum ions, Indicates the total amount.

In the case where the developing solution and the fixing solution according to the fourth aspect do not substantially contain a boron compound, the content of the developing solution and the fixing solution is preferably 0.1 to 0.1.
0001 mol / l. The boron compound is a generic term for compounds containing boron, such as boric acid and metaboric acid.

The fact that the fixing solution according to claim 5 does not substantially contain an acetate means that the content is less than 0.001 mol / l. The content of sulfite is 0.5
To 1.5 mol / l, preferably 0.6 to 1.
It is 2 mol / l, so that the effects of the present invention can be further enhanced. Sulfite refers to salts such as sodium sulfite and potassium sulfite.

The degree of swelling during the processing of the developing solution and the processing of the fixing solution according to the sixth aspect is defined as the value obtained from 5 seconds after the photosensitive material of the present invention is conveyed by an automatic developing machine and begins to be immersed in the developing solution, until the developing solution exits. Average degree of swelling over time, 4
It indicates the average degree of swelling between the time after the second and the time until it leaves the fixing solution.

The degree of swelling is a value obtained by dividing the value of {(b)-(a)} by (a) and multiplying the value by 100 when the dry film thickness (a) and the swelling film layer thickness (b) (%). ). Swelling degree is 100 ~
It is 200%, preferably 100-160%, from the viewpoint of exhibiting the effects of the present invention.

The light-sensitive material of the present invention may contain a hydrophilic polymer, and the content thereof is 3.5 g / side of the light-sensitive material.
m ² or less, preferably 1.0 g from the viewpoint of film physical properties and other factors.
/ M ² or more.

A silver halide emulsion layer of the light-sensitive material of the present invention,
One of the hydrophilic polymers used for the non-photosensitive hydrophilic colloid layer and the like is gelatin. Although other hydrophilic polymers are not particularly limited, dextran, dextrin, other polysaccharides, polyacrylic acids, and the like can be blended. In this case, those having an average molecular weight of 1,000 to 1,000,000 are preferably used. Especially, it is preferable to use 10,000 to 100,000 dextran. When blending gelatin and another hydrophilic polymer, 1
It is preferably from 50 to 50% by mass, more preferably from 5 to 20% by mass.

As the above gelatin, lime-treated, acid-treated or enzyme-treated gelatin is preferably used. Further, gelatin derivatives such as acetylated gelatin, phthalated gelatin, methyl esterified gelatin, and propyl esterified gelatin can also be used.

Among hydrophilic polymers other than gelatin, water-soluble polymers are preferable, and examples thereof include starch derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and sodium salt, polyacrylamide, dextrin, dextran, cyclodextrin, and carrageenan. .

The silver halide grains used in the light-sensitive material of the present invention are not particularly limited, but tabular silver halide grains having an aspect ratio of 3 or more are preferred. It is more preferably 3 or more and less than 15, and particularly preferably 3 or more and less than 8. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a silver halide grain to the distance (thickness) between two parallel main planes.

Tabular silver halide grains can be prepared, for example, by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution. The tabular silver halide grains may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is 0.2 to
It is preferably 0.5 mol%, and the conversion may be performed during physical ripening or after physical ripening.

As silver halide grains, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like can be used. The silver iodide content is preferably 2.0 mol% or less, more preferably 1.0 mol% or less, as the average silver iodide content of the whole silver halide grains.

Gelatin is preferably used as a dispersion medium for the protective colloid of silver halide grains. Examples of the gelatin include alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000), phthalated gelatin and the like. Is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Research Disclosur)
e, hereinafter abbreviated as RD) 176, 17643, IX (1
978 (Dec. 978). As for the amount of gelatin, the total amount of gelatin in all the hydrophilic colloid layers per one surface of the light-sensitive material is preferably 1.0 to 3.5 g / m ² .

Unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When the salts are removed, RD 176, 17
It can be carried out based on the method described in 643, section II.

The silver halide grains can be subjected to chemical sensitization. The conditions of the process of chemical ripening or chemical sensitization, for example, p
There are no particular restrictions on H, pAg, temperature, time, etc.
It can be performed under conditions generally performed in the art.
For chemical sensitization, use a sulfur-containing compound that can react with silver ions or active gelatin, a sulfur sensitization method using a selenium compound, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance. Reduction sensitization, gold and other, noble metal sensitization using a noble metal and the like can be used alone or in combination, among which selenium sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used, and in particular, Selenium sensitization is preferably used.

Regarding the selenium sensitizer, US Pat.
74,944, 1,602,592, 1,62
3,499, JP-A-60-150046, JP-A-4
-25832, 4-109240, 4-147
No. 250, etc.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), and selenoureas (N, N-dimethylselenourea, N, N, N'-triethyl). Selenourea), selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide, N, N-
Dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (tri-p-triselenophosphate, etc.), selenides (diethylselenide) , Diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. The method of addition depends on the nature of the selenium compound used, such as water or methanol, ethanol,
The method disclosed in Japanese Patent Application Laid-Open No. 4-140739, namely, a method in which the organic solvent such as ethyl acetate is dissolved alone or in a mixed solvent, or a method in which the organic solvent is previously mixed with a gelatin solution and added, is used. A method of adding in the form of an emulsified dispersion of a mixed solution with a solvent-soluble polymer may be used.

The silver halide emulsion may be spectrally sensitized with a cyanine dye or the like. The sensitizing dye may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for supersensitization.

When the light-sensitive material of the present invention is used as a medical double-sided emulsion X-ray light-sensitive material, it is preferable to provide a transverse light blocking layer for the purpose of improving image sharpness. The transverse light blocking layer contains a solid fine particle dispersion of a dye for the purpose of absorbing transverse light. Such a dye is not particularly limited as long as it has a structure which is soluble in an alkali having a pH of 9 or more and has a structure which is hardly soluble at a pH of 7 or less. The compound of the general formula (I) described in JP-A-30870 is preferably used. X
When used as a line light-sensitive material, a material commonly used as a fluorescent intensifying screen when exposing X-rays can be used.

Various photographic additives can be used in the photographic material before and after physical ripening or chemical ripening of the silver halide emulsion.

Compounds that can be used in such a step include, for example, RD17643 (supra), RD18716
No. (November 1979) and RD308119 (19
(December 1989).

As the support used in the light-sensitive material of the present invention, those described in the above RD can be mentioned. A suitable support is a plastic film or the like, and the surface of the support has good adhesion of the coating layer. For this purpose, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied. Then, a silver halide emulsion can be coated on both surfaces of the support thus treated.

The photosensitive material may be provided with an antihalation layer, an intermediate layer, a filter layer and the like, if necessary.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive material can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method and the like can be used. For details, see "Coatingpr" in RD 176, pp. 27-28.
methods may be used.

The drying conditions when the photosensitive material is coated and dried are preferably a drying time of 1 to 5 minutes and a wet bulb temperature of not more than 1000% and a wet bulb temperature of 15 to 30 ° C.

The processing method for a light-sensitive material of the present invention exhibits excellent performance in rapid development processing by an automatic processor in which the total processing time is 15 to 60 seconds, more preferably 15 to 30 seconds.

As the developer in the developing process, usually,
For black and white photography, for example, reductones (such as erythorbic acid), dihydroxybenzenes, 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), and aminophenols (such as N-methyl-aminophenol) alone or in combination Can be used. In the invention of claim 1, reductones are used, and the effect of the present invention is exhibited. However, it is preferable that the inventions of other claims also contain reductones, and that the invention does not substantially contain dihydroxybenzenes. preferable.

In the developer, JP-A-6-13 was used as a preservative.
In addition to the sulfite described in No. 8591, an organic reducing agent can be used. In addition, a bisulfite adduct of a chelating agent or a hardener described in JP-A-6-13891 can be used. Also, JP-A-5-289255, JP-A-6-308
No. 650, described in JP-A-1-124.
It is also preferable to add a cyclodextrin compound described in No. 853 and an amine compound described in US Pat. No. 4,269,929.

Further, it is necessary to use a buffer in the developing solution. Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The necessary buffer can be selected according to the configuration of the invention.

Further, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds,
Polyalkylene oxide, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be used as necessary. As antifoggants, alkali metal halides such as potassium iodide, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole , 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, adenine and the like organic antifoggants can be used.

The developer further includes methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, JP-B-47-33378 and JP-B-44-378.
The compound described in No. 9509 can be used as an organic solvent for increasing the solubility of the developing agent. In addition, a stain inhibitor, a silver sludge inhibitor, and a multilayer effect promoter can also be used.

Known compounds such as a fixing agent, a chelating agent, a pH buffer and a preservative can be used in the fixing solution. For example, JP-A-4-242246 or JP-A-5-11363 can be used.
No. 2 can be used.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

As a preferred embodiment of the treatment method of the present invention,
At least one of the developer and the fixer dissolves the solid agent;
There is a form which is a liquid prepared by dilution. The solid agent is a solid processing agent, and its form includes tablets, pills, granules, powders and the like. Here, the powder is an aggregate of fine crystals, the granule is a granulated powder, and is generally a granular material having a particle size of 50 μm or more and 1000 μm, and the tablet is a powder or a granule having a certain size. It is compression molded into a shape.

The amount of the solid agent supplied at one time is preferably 1 g or more from the viewpoint of quantitativeness, and 20 g or less is preferable from the viewpoint of stability of the developer concentration. In particular, within this range,
Even if the solid agent is replenished directly to the developer and processed while slowly dissolving, it does not adversely affect the photographic condition. This is because the solid agent does not dissolve rapidly but dissolves slowly, so that even if the amount added at a time is large, the composition balances with the amount consumed during processing.

It is preferable that the solid agent is previously divided and weighed into a predetermined amount. `` Pre-divided and weighed '' means that the solid agent has already been divided and weighed to a predetermined fixed amount before setting the solid agent in the automatic processing machine, for example, formed into tablets or pills of a predetermined size. And a mode in which granules or powder are subdivided into predetermined amounts and packaged. If the solid agent is divided and weighed in a predetermined amount in advance, replenishment accuracy is high and extremely stable continuous processing performance is exhibited.

As a method for producing a tablet, a method of granulating a powdered solid agent and then tableting is preferred from the viewpoints of solubility, storage stability and photographic performance stability. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. Next, when the obtained granules are tableted, a known tableting machine, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used.

Tablets and pills can be moisture-proof by coating with a water-soluble moisture-proof polymer, or by using a moisture-proof material. For powders and granules, select a moisture-proof material for each packaging material. It is moisture-proof by doing.

In the case of processing using a processing solution prepared from a solid agent, it is desirable to replenish water to the developing solution according to the development processing amount of the silver halide black-and-white photographic light-sensitive material. In this case, an automatic developing machine is provided with a processing amount detection means for detecting the development processing amount of the silver halide black-and-white photographic light-sensitive material, and according to the development processing amount of the silver halide black-and-white photographic light-sensitive material detected by the processing amount detection means. It is desirable to control the supply of the solid agent to the developer and the replenishment of water to the developer. in this case,
Replenishment of the water developer is performed for the following three purposes. First, the concentration of the accumulation harmful suppressing component eluted by the reaction during the processing of the silver halide black-and-white photographic light-sensitive material is adjusted to be constant, and secondly, the moisture taken out by the processed silver halide black-and-white photographic light-sensitive material. Alternatively, it is to dilute and dilute unnecessary chemicals brought in from the previous liquid, and thirdly, to supply water evaporated from the tank surface. Water may be supplied from a rehydration tank.

The place where the solid agent is supplied may be any place in the processing liquid, but is preferably a place where the processing liquid communicates with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, it is preferable that there is a certain processing liquid circulation amount between the processing unit and the dissolved component moving to the processing unit. The solid agent is preferably introduced into the processing solution whose temperature is controlled.
Generally, the temperature of an automatic processor is controlled by an electric heater, and the temperature of the processing solution is controlled by an electric heater.A heat exchange unit is provided in an auxiliary tank connected to the processing tank as a processing unit, and a heater is installed. A pump is arranged so that the liquid is sent from the tank at a constant circulation amount and the temperature is kept constant. The most preferable method is to supply the solid agent to a place where the temperature is controlled, such as the auxiliary tank, which is in communication with the processing unit.

It is preferable that a filter is disposed in the auxiliary tank for the purpose of removing foreign substances mixed in the processing liquid. Because the insoluble component of the supplied processing agent is cut off from the processing unit by the filter unit,
This is because it is possible to prevent the insoluble component from flowing into the processing section and attaching to the photosensitive material or the like.

The circulation frequency of the circulating developer is preferably 0.5 times / minute or more (especially 0.8 times / minute or more, more preferably 1.0 times / minute or more), and 2.0 times / minute. The following is preferred. As a result, the dissolution of the solid agent is promoted, the generation of a high-concentration liquid portion of the developing solution can be prevented, the occurrence of concentration unevenness in the processed photosensitive material can be prevented, and the generation of insufficiently processed photosensitive material can be prevented. Can be prevented.

[0089]

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 Hereinafter, unless otherwise specified, "%" in Examples indicates "% by mass".

<Preparation of Seed Emulsion-1> A1 Ossein gelatin 24.2 g Distilled water 9657 ml Surfactant AO-1 (10% methanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5 mol / L silver nitrate aqueous solution 2825 ml C1 Potassium bromide 841 g Finish up to 2825 ml with water D1 1.75 mol / L aqueous potassium bromide solution Silver potential control amount below AO-1: Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt 42 ° C. Nos. 58-58288 and 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of the solution (B1) and the solution (C1) was added to the solution (A1) by a simultaneous mixing method over 1.5 minutes, and nucleation was carried out. went.

After stopping the addition of the solution (B1) and the solution (C1), it takes 40 minutes to raise the temperature of the solution (A1) to 50 ° C., and to adjust the pH to 5 with a 3% aqueous potassium hydroxide solution. After that, the solution (B1) and the solution (C1) were adjusted again.
Was added at a flow rate of 55.4 ml / min for 42 minutes by the double jet method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 50 ° C. and the re-mixing with the solutions (B1) and (C1) was measured. +8 using D1)
mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with a 3% aqueous solution of potassium hydroxide, and immediately desalting and washing were performed. This seed emulsion-1 is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 at 90% or more of the total projected area of the silver halide grains, an average thickness of 0.045 μm, and an average grain size of 0.045 μm. It was confirmed by an electron microscope that the diameter (in terms of circular diameter) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

<Preparation of tabular silver bromide emulsion>
A tabular pure silver bromide emulsion was prepared using the following three solutions. A2 Ossein gelatin 34.03 g Surfactant AO-1 (10% aqueous methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water B2 1747 g Potassium bromide Equivalent to 3669 ml with water 2493 g water silver nitrate In the reaction vessel, the solution (A2) was vigorously stirred while maintaining it at 50 ° C., and the total amount of the solution (B2) and the solution (C2) was reduced to 1 in the reaction vessel.
It was added by the double-mixing method over 00 minutes. During this time, the pH was kept at 9.0 with an aqueous potassium hydroxide solution, and the pAg was kept at 8.6 throughout. Here, the solution (B2) and the solution (C
The addition rate of 2) was changed functionally with respect to time to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multi-components due to Ostwald ripening.

After completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregating polymer, and the mixture was added for 3 minutes. Stirred. Then 5
The pH of the emulsion was adjusted to 4.6 by adding a 6% acetic acid aqueous solution, stirred for 3 minutes, allowed to stand for 20 minutes, the supernatant was drained by decantation, and 11.25 L of distilled water was further added.
, And the mixture was stirred and allowed to stand, and then the supernatant was drained.

Subsequently, an aqueous solution of gelatin and an aqueous solution of 10% sodium carbonate were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redistribution, 4
The pH was adjusted to 5.80 and the pAg to 8.06 at 0 ° C.

When the obtained silver bromide emulsion was observed with an electron microscope, the average particle diameter was 0.84 μm and the average thickness was 0.16.
μm, average aspect ratio about 5.3, particle size distribution width 20
% Tabular grains. The amount of gelatin at the end of the physical ripening was 15.9 g per mol of silver halide.

<Preparation of Silver Halide Emulsion A> The emulsion prepared above was heated to 55 ° C., 11.3 mg of adenine per mol of silver halide, and 450 spectral sensitizing dyes (A) shown below.
mg and 45 mg of spectral sensitizing dye (B), and 100 mg of stabilizer (ST-1) were further added. After 10 minutes, 3.5 mg of chloroauric acid and 10 mg of sodium thiosulfate were added.
mg and 100 mg of ammonium thiocyanate.
After a further 40 minutes, the following silver iodide fine grain emulsion was added to a silver iodide 0.
3 mol equivalent amount, and 10 minutes later, 5 mg of triphenylphosphine selenide was added, and 40 minutes later (ST
-1) 500 mg was added, and after 5 minutes, 13 g of trimethylolpropane and 30 g of gelatin were added, followed by rapid cooling to gel the emulsion to complete the chemical sensitization. This emulsion is designated as silver halide emulsion A.

Sensitizing dye (A): 5,5'-di-chloro-
Anhydride of sodium salt of 9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl -3,3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene <Preparation of silver iodide fine particles> A3 ossein gelatin 100 g Potassium iodide 8.5 g Make up to 2000 ml with distilled water B3 Silver nitrate 360 g Make up to 605 ml with distilled water C3 352 g Potassium iodide 605 ml with distilled water The solution (A3) was added to the reaction vessel, and the solution (B3) and the solution (C3) were added at a constant speed by a simultaneous mixing method over 30 minutes while stirring at 40 ° C. The pAg during the addition was kept at 13.5 by a conventional pAg control means.

The resulting silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion.

<Preparation of Subbed Support> Thickness 175 μm
After a corona discharge treatment of 8 Wmin / m ² was applied to both sides of a polyethylene terephthalate (PET) base colored blue at a concentration of 0.20 with an undercoat, an undercoat was applied.
After drying for a minute, a subbed support was obtained.

<Preparation of photosensitive material> The following first to third layers were simultaneously coated on both sides of the obtained undercoated support as the first layer from the side closer to the support (dye layer). did.

[0103] The first layer (dye layer) indicating the amount of one side 1 m ² per each material.

Lime-treated inert gelatin 0.1 g / one side m ² Filter dye F (solid dispersion) 70 mg / one side m ² Polymer latex L (glass transition point 40 ° C.) 70 mg / one side m ² Viscosity modifier V-1 Viscosity 10 mPa · s and qs second layer (emulsion layer) silver halide emulsion a silver amount as 1.35 g / one side m ² hydrophilic polymer: lime-treated inert gelatin and dextran (average molecular weight: 40,000) is 90:10 ratio 1 0.9 g / m ^{2 on} one side 1,1-dimethylol-1-bromo-1-nitromethane 70 mg / AgX mol Nitrophenyl-triphenylphosphonium chloride 2.8 mg / AgX mol C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 1.0 g / AgX mol Antifoggant (AF-1) 8.5 mg / AgX mol Colloidal silica (ヂ13 g / AgX mol 150 mg / AgX mol 1,3-dihydroxybenzene-4-sulfonic acid ammonium 1.7 g / AgX mol Antifoggant (AF-2) 15 mg / AgX mol thallium nitrate 55 mg / AgX mol Trimethylolpropane 6.5 g / AgX mol Viscosity modifier (V-1) Amount that gives a viscosity of 30 mPa · s Third layer (protective layer) Except for the hardener, the amount is shown per 1 m ² per side.

[0105] lime-treated inert gelatin 0.6 g / one side m ² Sodium-dihexyl sulfosuccinate 5mg / single-sided m ² Sodium · (amyl-decyl) sulfosuccinate 3 mg / simplex _{^{m 2 C 11 H 23 CONH (}} CH 2 CH 2 O) ₅ H 5 mg / one side m ² Sodium di (2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl) sulfosuccinate 1.2 mg / one side m _{^{2 p-C 8 H 17 -C}} 6 H 4 -O (CH 2 CH 2 O) 4 -SO 3 Na 15mg / single-sided _{^{m 2 C 16 H 33 O (}} CH 2 CH 2 O) 10 H 15mg / single-sided m ² _{C 11 H 23 CON [(CH} 2 CH 2 O) m H] (CH 2 CH 2 O) n H (m + n = 10) 40mg / single-sided m ² fluorine-based surfactant (compound represented by formula (1), (Compound of (2) and Comparative Compound) (Table 1) Description) Amount described in Table 1 Antifoggant (AF-3) 3 mg / one-sided m ² Preservative (DF-1) 1 mg / one-sided m ² Matting agent composed of polymethyl methacrylate (average particle size 3.3 μm) 30 mg / one-sided m ^{2 The} hardener (H-1) was added in an amount of 25 mg / g to all the hydrophilic polymers in 1 to 3 layers.

V-1: Sodium polystyrene sulfonate (Mw = 500,000) AF-1: 1-Phenyl-5-mercaptotetrazole AF-2: 1- (3-Sodium sulfonatophenyl)-
5-mercaptotetrazole AF-3: 1- (4-sodiumcarboxylatophenyl) -5-mercaptotetrazole H-1: 1,2-bis (vinylsulfonylacetamide) ethane

[0107]

Embedded image

<Preparation of processing agent><Preparation of solid developer α using hydroquinone as a developing agent> A solid developer α was prepared according to the method described below.
In addition, the displayed value is 1 when used as a developer.
It is equivalent to 00 liters.

(Preparation of Granulated Material A) Hydroquinone (hereinafter abbreviated as HQ) 3000 g, phenidone 400 g, boric acid 1000 g, N-acetyl-D, L-penicillamine 1
0 g and sodium glutaraldehyde bisulfite 800
g in a commercially available bantam mill, each having an average particle size of 1
Crushed to 0 μm. 700 g of sodium sulfite and 200 g of D-sorbit as a binder were added to this fine powder.
, And mixed in a bantam mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 5 minutes in a commercially available stirring granulator. For 2 hours to remove the water content of the granulated product almost completely, thereby producing a granulated product A.

(Preparation of granulated substance B) Potassium carbonate 5300
g, potassium bicarbonate 50 g, potassium bromide 200 g,
Each was pulverized in a commercially available bantam mill until the average particle size became 10 μm. 200 g of lithium hydroxide hydrate and diethylene-triaminepentaacetic acid (DTP) were added to this fine powder.
A.5H) 250 g, 1-phenyl-5-mercaptotetrazole 5 g, sodium sulfite 4000 g, and binder mannitol 1000 g were added, and the mixture was added to a bantam mill.
After mixing and granulating by adding 30 ml of water for about 15 minutes at room temperature in a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours by a fluidized bed drier. The water in the granulated product was almost completely removed, and a granulated product B was produced.

(Preparation of Solid Developer α) The above granulated materials A and B
Sodium 1-octanesulfonate was added to each so as to be 3% of the mass of each, and 2
After uniformly mixing for 10 minutes using a mixer in a room humidified at 5 ° C. and 40% RH or less, each of the obtained mixtures was mixed with a tableting machine modified from Tough Press Collect 1527HU (manufactured by Kikusui Seisakusho Co., Ltd.). Each tablet was adjusted so as to have a filling amount of 10.09 g for the granulated product A and 9.5 g for the granulated product B, and compression tableting was performed. Was prepared. Each of the tablets A and B was sealed and packaged in a pillow bag containing aluminum for moisture proofing in an amount equivalent to 3.5 liters of a developing solution. These are referred to as solid developers α.

<Erythorbic acid (Exemplified compound 3 of the present invention)
Preparation of solid developer β using -1) as a developing agent> A solid developer β was prepared according to the method described below. In addition, the displayed numerical value is the amount of 100 liters when used as a developer.

(Preparation of granulated product C) 400 g of phenidone,
10 g of N-acetyl-D, L-penicillamine and 800 g of sodium glutaraldehyde bisulfite are each ground in a commercially available bantam mill to an average of 10 μm. To this fine powder, 1500 g of sodium metabisulfite, 6800 g of sodium erythorbate (hereinafter abbreviated as ER), and 600 g of a binder D-sorbite were added, mixed in a mill for 30 minutes, and mixed at room temperature in a commercial stirring granulator. 30 minutes for 10 minutes
After granulation by adding water, the granulated product was dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the moisture of the granulated product, thereby producing a granulated product C. .

(Preparation of Granules D) Potassium carbonate 1030
0 g and 100 g of potassium bicarbonate were each pulverized in a commercially available bantam mill until the average particle size became 10 μm.
To this fine powder, 500 g and 950 g of diethylene-triamine sodium pentaacetate (DTPA · 5Na), 40 g of the following compound AF-1, 10 g of the following compound AF-2,
7 g of potassium iodide, methyl-β-cyclodextrin 2
Then, 2000 g of mannitol and 700 g of D-sorbite were added as binders, mixed in a bantam mill for 30 minutes, and placed in a commercially available stirring granulator at room temperature for about 15 minutes.
After granulating by adding ml of water, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the water content of the granulated product to produce a granulated product D did.

Compound AF-1: sodium 1- (3-sulfophenyl) -5-mercaptotetrazole Compound AF-2: sodium 5-mercapto- (1H) -tetrazolylacetate (Preparation of solid developer β) Sodium 1-octanesulfonate was added to each of the products C and D so as to make 1.3% of the mass of each, and 25
After uniformly mixing for 10 minutes using a mixer in a room conditioned at 40 ° C. or less at 40 ° C., 10.0 g of granulated material C and granulated material were filled in the same manner as the solid developer α. D is 1
The tablets were compressed and compressed to 0.0 g to produce cylindrical developing tablets having a diameter of 30 mm. The tablets C and D thus prepared were sealed in a pillow bag containing aluminum in an amount equivalent to 3.5 liters of the developing solution for moisture prevention. These are referred to as solid developers β.

<Preparation of solid fixing tablet> A solid fixing tablet corresponding to 100 liters as a fixing solution was prepared according to the method described below.

(Preparation of Granulated Material E) Ammonium thiosulfate / sodium thiosulfate (90/10 mass ratio) 15000
g was ground in a commercially available bantam mill until the average particle size became 10 μm. Sodium metabisulfite 9
00 g, 1300 g of pine flow as a binder,
50 ml of water was added to perform stirring and granulation, and the granulated product was dried at 40 ° C. using a fluidized bed drier to almost completely remove water, thereby producing a granulated product E.

(Preparation of Granulated Material F) Aluminum Sulfate · 8
1500 g of water salt, 1200 g of succinic acid, 250 g of boric acid, 300 g of tartaric acid and 200 g of sodium gluconate were ground in a commercially available bantam mill until the average particle size became 10 μm. 250 g of D-mannitol and 120 g of D-sorbite are added to this fine powder, and 30 ml of water is added to carry out stirring granulation, and the granulated material is dried at 40 ° C. in a fluidized bed drier to almost completely remove water. After removal, a granulated material F was produced.

The granulated product E prepared as described above was added to β
3000 g of alanine, 1400 g of sodium acetate, and sodium 1-hexanesulfonate in a total mass of 3.0 g.
%, And to the granulated product F, 1500 g of sodium acetate and sodium 1-hexanesulfonate were added so as to be 3.0% of the total mass.
Using a mixer in a room humidified to 40% RH or less
After uniformly mixing for 0 minutes, each of the obtained mixtures was converted into a granule E in an amount of 1 per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed so that 0.2 g of the granulated product F and 11.2 g of the granulated product F were prepared, thereby producing cylindrical solid fixing tablets having a diameter of 30 mm.

Each solid fixing tablet was sealed and packed in a pillow bag containing aluminum in an amount equivalent to 3.5 liters of fixing solution to prevent moisture. These are designated as solid fixing tablets (E + F). <Processing and Evaluation> The photosensitive material obtained above was subjected to uniform exposure so as to have a density of 1.0, and was subjected to automatic developing machine TCX-201 (manufactured by Konica Corporation) and SRX-101.
Using Konica Corporation, a running process was performed.

For TCX-201, the operating time per day is 24 hours, and the size of the quadruple per day is 20 hours.
Zero-sheet processing was continued for three months. The standby time is 30
Minutes.

For the SRX-101, the operating time per day is 10 hours, and the size per quarter per day is 6
The sheet processing was continued for 6 months. The standby time was 10 minutes.

The processing conditions are as follows. TCX-201 SRX-101 Developing temperature 36 ° C 34 ° C Fixing temperature 36 ° C 34 ° C Washing temperature 18 ° C (tap water temperature) 18 ° C (tap water temperature) Drying temperature 55 ° C 55 ° C Processing time 60 seconds 90 seconds Replenishment amount (development / Fixing) 180/180 (ml / m ² ) 180/180 (ml / m ² ) SRX-101 has an opening ratio (opening area /
(Volume) was adjusted to 0.01 by adding an antioxidant plate to the developing rack and the tank. It was confirmed that the remodeling did not affect the development processability.

As a chemical mixer, TCX-M50 is used.
(Manufactured by Konica Corporation) was remodeled into a small size so that 3.5 L of the developing solid agents α and β and the fixing solid agent could be dissolved, and a sub-tank tank for supplying a replenisher (tank stocked after the preparation: 7)
An antioxidant plate was provided so that the opening ratio of (L volume) was 0.005 or less. After the solid agent is prepared by the chemical mixer, it is moved to the sub tank and supplied as a replenisher. When the remaining volume of the processing liquid in the sub tank reaches 3.0 L, the next 3.5 L of the solid agent is prepared by a chemical mixer. The TCX-201 was originally an internal chemical mixer type, but was changed to an external chemical mixer specification and connected to the modified TCX-M50 (chemical mixer).

In the case of TCX-201, 7.8 L of development replenisher was added, and a starter described later was added to fill the developing tank as a start solution. In the case of SRX-101, 3.9 L of development replenisher was added. Add the same starter and fill the developing tank as a start solution.
The fixing solution was filled with 7.5 L in the case of CX-201 and 1.9 L in the case of SRX-101. Regarding the pH of the development start solution, in the case of TCX-201, pH 9.8.
0 and SRX-101, pH 9.60.

(Starter Formulation) Amount Added to 1 L of Developer 5.5 g of Potassium Bromide HO-CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ —OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite Amount to be the pH of the starting solution 60 ml finished with water <Evaluation of density unevenness> Prepare three large-size sheets uniformly exposed to densities of 1.0, 1.35 and 1.7, and prepare an automatic developing machine T
The CX-201 was processed after 1 month and 3 months, and the automatic developing machine SRX-101 was processed after 3 months and 6 months. Density unevenness was visually evaluated according to the following evaluation criteria.

5: No unevenness in density was observed. 4: Somewhat seemed to be uneven, but there was no problem in diagnosis. 3: Unevenness in density occurred at a partially low density. Level near the lower limit of practical use 2: Density unevenness occurs over the entire surface at low density 1: Density unevenness occurs over the entire surface at high density <Evaluation of image defects and failure of unexposed film> Three months with TCX-201 automatic developing machine The following three days are selected, and in the automatic developing machine SRX-101, the three days after six months are selected, and the film which is running during the three days (the uniform exposure is performed so that the density becomes 1.0) ) Were randomly selected from 10) to evaluate image defects.

At the same time, the unexposed film was processed to evaluate the failure of the unexposed film such as adhesion of silver sludge and remaining emulsion due to crystal attachment. Evaluation criteria for image defects 5: No spot defects at all, no stains found 4: No spot defects that could interfere with diagnosis, but partial stain adhesion 3: Density at edges Some spots are missing (pocket-like defects), and some dirt is adhered. 2: Spot-like defects such as missing density or high density are observed, and the size of the spots is small but slightly larger. : Many large spot defects (loss of density, increase in density (+0.5)) are observed on the entire surface, and silver sludge adheres frequently. Evaluation criteria for failure of unexposed film 3: No silver sludge adheres and no emulsion remains 2 : A few emulsion residues remained in several places. 1: A large amount of silver sludge adhered, and emulsion residues were observed on the entire surface.

[0129]

[Table 1]

As shown in Table 1, in the case of the structure according to the first aspect of the present invention, it can be seen that the effects of improving density unevenness, image defects, and film failure are exhibited.

That is, as in the constitution of the first aspect of the present invention, a reductone (particularly erythorbic acid, It can be seen that by processing with a developing solution containing (ascorbic acids) as the principal agent, there is no failure due to adhesion caused by processing components, density unevenness is largely suppressed, and image quality is excellent.

Example 2 A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1, except that the compound represented by the general formula (1) or (2) was selected as shown in Table 2. .

A fixing agent was prepared in the same manner as in Example 1 except that ammonium thiosulfate in the components of the fixing agent was used in the same manner as in the content of thiosulfate of the type shown in Table 2 except that the content was changed. .

Running was performed in the same manner as in Example 1 on TCX-201 and SRX-101.
Image defects after 6 months and failure of the unexposed film were evaluated.

Table 2 shows the above progress and results.

[0136]

[Table 2]

As shown in Table 2, it can be seen that the constitution of the second aspect of the present invention has an excellent effect of improving image defects and failure of unexposed films.

That is, as in the constitution of the second aspect of the present invention, a photosensitive material containing a compound represented by the general formula (1) or (2) is used to substantially contain an ammonium salt. By processing using a developer and a fixer that do not
It can be seen that a failure due to the fixing process is prevented and the image quality is improved. This is due to the effect particularly exhibited by the combination of the light-sensitive material containing the compound of the present invention and the ammonia-free processing solution.

Example 3 For the developer, the amount of glutaraldehyde sodium bisulfite was changed as shown in Table 3, and the amount of the solid aluminum sulfate and pH for the fixing agent were changed as shown in Table 3. In the same manner as in Example 1, a developer and a fixing agent were prepared.

Running was performed in the same manner as in Example 1 on TCX-201 and SRX-101.
After a month, image defects were evaluated in the same manner.

Further, the processed running film was observed, and the drying unevenness including the unevenness caused by the gloss unevenness and the drying air was visually evaluated according to the following criteria.

<Evaluation of Drying Unevenness> 5: Neither transmission unevenness nor reflection unevenness was observed, and the image quality was good. 4: There was no transmission unevenness, but reflection unevenness with extremely low density was observed in a minute range. 3: No transmission unevenness was observed. However, reflection unevenness is partially observed, and the lower limit of practical use in terms of image quality 2: there is no transmission unevenness, but reflection unevenness is clearly observed over the entire surface. 1: transmission unevenness and reflection unevenness are both observed. It is shown in Table 3.

[0143]

[Table 3]

As shown in Table 3, it can be seen that in the case of the constitution of the third aspect of the present invention, the effect of improving image defects and uneven drying is excellent.

That is, as in the constitution of the third aspect of the present invention, a photosensitive material containing a compound represented by the general formula (1) or (2) is used, and a glutaraldehyde compound is substantially contained. By using a developing solution that does not contain aluminum oxide and a fixing solution that does not substantially contain aluminum ions, remarkable crystallization and film failure due to silver sludge are eliminated, unevenness due to drying is greatly improved, and image quality is improved. You can see that. This is because self-condensation is achieved by freeing (substantially not containing) the hardening component of the developer and fixer.
This is because the generation of by-products and the like can be eliminated, and the effect is particularly exhibited by the combination with the photosensitive material containing the compound represented by the general formula (1) or (2).

Example 4 A developer and a fixing agent were prepared in the same manner as in Example 1 except that the amounts of the boron compound of the developer and the fixing agent were changed as shown in Table 4.

In the same manner as in Examples 1 and 3, TCX-2
01 and SRX-101 to evaluate density unevenness and drying unevenness.

Table 4 shows the above progress and results.

[0149]

[Table 4]

As shown in Table 4, it can be seen that in the case of the constitution of the fourth aspect of the present invention, the effect of improving density unevenness and drying unevenness is excellent.

That is, as in the constitution of the fourth aspect of the present invention, a light-sensitive material containing a compound represented by the general formula (1) or (2) is used and contains substantially no boron compound. By processing with a developer and a fixer, it is possible not only to reduce substances that fall under the regulations of the Water Pollution Control Law and contribute to improving water quality, but also to improve density unevenness and drying unevenness caused by the developing tank and improve image quality. It turns out that it improves. This is due to the effect particularly exhibited by the combination of the treatment solution containing no boron compound and the compound represented by the general formula (1) or (2).

Example 5 The amount of sodium acetate as the fixing agent in Example 1 was changed to the amount shown in Table 5, and the type and amount of sulfite were changed as shown in Table 5.
A fixing agent was prepared in the same manner as in Example 1 except that the fixing agent was changed as described.

In the same manner as in Example 1, TCX-201, S
Processing was performed by RX-101, and image defects were evaluated.

Further, as a measure of fixability, the evaluation of residual silver when an unexposed film was processed was performed as follows.

<Evaluation of Residual Silver> One drop of a 2.6 × 10 ⁻³ mol / L aqueous solution of sodium sulfide (residual silver evaluation liquid) was dropped on the obtained unexposed sample, and after leaving for 3 minutes, the liquid was wiped off. And allowed to stand at room temperature and humidity for 15 hours. Thereafter, the transmission density of blue light in the portion where the residual silver evaluation solution was dropped and the portion where the remaining silver was not dropped was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and the difference was used as a guide for the residual silver. If the value is 0.03 or less, there is no problem, but if it is more than 0.03, the silver image is discolored with time and the density is reduced.

Table 5 shows the above progress and results.

[0157]

[Table 5]

As shown in Table 5, in the case of the constitution of the fifth aspect of the present invention, it can be seen that the image defect is improved and the fixability (the residual silver is improved) is excellent.

That is, as in the constitution of the fifth aspect of the present invention, a photosensitive material containing a compound represented by the general formula (1) or (2) is used, and an acetate is substantially contained. Treatment with a fixing solution containing 0.5 to 1.5 mol / L of sulfite not only improves the odor of the processing solution itself, but also eliminates breakdown due to crystallization and silver sludge generation. It can be seen that the image quality is greatly improved.
Further, the fixing property was also improved. This is because even if acetate which has been used as a fixing buffer agent is replaced with sulfite,
This is due to the effect particularly exhibited by combining with the compound represented by the general formula (1) or (2).

Example 6 The same procedure as in Example 6 was carried out except that the swelling degree during the processing with the developing solution and the processing with the fixing solution were changed as shown in Table 6 with respect to the concentration of the hardener and the amount of gelatin in the protective layer of the photographic material. In the same manner as in Example 1, a light-sensitive material was prepared.

In the same manner as in Examples 1 and 3, TCX-20
1. Processing was performed by SRX-101, and image defects, development unevenness, and drying unevenness were evaluated.

Table 6 shows the above progress and results.

[0163]

[Table 6]

As shown in Table 6, in the case of the constitution of the sixth aspect of the present invention, it can be seen that excellent improvement effects on image defects, development unevenness and drying unevenness are exhibited.

That is, as in the constitution of the sixth aspect of the present invention, a photosensitive material containing a compound represented by the general formula (1) or (2) is used during processing in a developing solution and processing in a fixing solution. By adjusting the degree of swelling in the medium to 100 to 200%, it is found that the film failure is prevented and the image quality of development unevenness and drying unevenness is greatly improved. Silver sludge,
It can be seen that the occurrence of crystallization is reduced even under severe processing conditions. This is due to the fact that the degree of swelling could be controlled and the effect particularly exhibited by the combination of the compound represented by the general formula (1) or (2) and the treatment liquid.

[0166]

According to the present invention, when processing a silver halide photographic light-sensitive material with an automatic processor, severe processing conditions such as low replenishment of processing solutions, long-term continuous processing, and concentration of processing solution fatigue. Density unevenness that is fatal in diagnosis, which is likely to occur in
It is possible to provide a method for processing a silver halide photographic material in which the occurrence of density defects due to silver sludge and crystal adhesion is improved.

Claims (7)

[Claims] 1. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic processor having at least a developing solution, a fixing solution and washing water. In the processing method, the light-sensitive material contains a compound represented by the following general formula (1) or (2), and the developer contains reductones. . Formula (1) Rf- 'in _n -L ₁ -X _m [wherein, Rf represents an aliphatic group containing at least one fluorine atom, Rf (O-Rf)' is at least one fluorine atom N and m are each 1
L ₁ represents a simple bond or a linking group, and X represents a hydroxy group, an anionic group or a cationic group. General formula (2) [(Rf "O) _n1- (PFC) -CO-Y ₁ ] _k -L _2-
X ′ _m1 [wherein, Rf ″ represents a perfluoroalkyl group having 1 to 4 carbon atoms, (PFC) represents a perfluorocycloalkylene group, and Y ₁ represents a linking group containing an oxygen atom or a nitrogen atom. L ₂ represents a simple 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;
Represents an integer of 1 to 5, k represents an integer of 1 to 3, and m1
Represents an integer of 1 to 5. ] 2. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. In the processing method, the light-sensitive material contains the compound represented by the general formula (1) or (2), and the developing solution and the fixing solution contain substantially no ammonium salt. Processing method of photographic photosensitive material. 3. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic processor having at least a developing solution, a fixing solution and washing water. In the processing method, the photosensitive material contains the compound represented by the general formula (1) or (2), the developer contains substantially no glutaraldehyde compound, and the fixer contains aluminum ions substantially. A method for processing a silver halide photographic light-sensitive material, characterized in that the light-sensitive material is not contained. 4. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic processor having at least a developing solution, a fixing solution and washing water. In the processing method, the light-sensitive material contains a compound represented by the general formula (1) or (2), and the developing solution and the fixing solution contain substantially no boron compound. Processing method of photographic photosensitive material. 5. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. In the processing method, the light-sensitive material contains the compound represented by the general formula (1) or (2), and the fixer contains substantially no acetate, and contains 0.5 to 1. A method for processing a silver halide photographic light-sensitive material, characterized by containing 5 mol / L. 6. A silver halide photographic material having a silver halide photographic emulsion layer and a non-photosensitive hydrophilic colloid layer on a support is processed by an automatic developing machine having at least a developing solution, a fixing solution and washing water. In the processing method, the light-sensitive material contains a compound represented by the general formula (1) or (2), and the swelling degree of the light-sensitive material during processing with a developing solution and processing with a fixing solution is 100 to 200%. A method for processing a silver halide photographic material. 7. A developer and a fixer each comprising a solid developer,
The method for processing a silver halide photographic material according to any one of claims 1 to 6, wherein the solid fixing agent is dissolved.