Claims
- 1. A method for developing an exposed high contrast photographic material, said photographic material comprising a support bearing at least one silver halide emulsion layer, containing at least one hydrazide nucleating agent, characterized in thata) said nucleating agent has the formula (I): wherein each A1 and each A2 is independently selected from the class consisting of a hydrogen atom, or a substituted or unsubstituted acyl, or alkyl- or aryl-sulfonyl group; each Y is independently selected from a substituted or unsubstituted aryl or heterocyclic ring or ring system; each X is independently selected from S═O, C, C—NH and C—O; each L′ is independently selected from a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl or heterocyclic ring or ring system linked to Z via a substituted or unsubstituted alkylene group either directly or via a group selected from NR1CO—, NR1CONR2—, OCONR1— or NR1COO—, wherein R1 and R2 are independently selected from a hydrogen atom or a substituted or unsubstituted alkyl group; each Z is independently selected from an unsubstituted or substituted group, ring or ring system attached via a heteroatom selected from sulfur, nitrogen, oxygen or phosphorus; each L is independently a divalent, trivalent or tetravalent linking group; p and each n are independently 0 or 1 k is an integer from 0 to 8; and m is an integer from 2 to 4 provided that when p is 0, n is 0 and m is 2; when p is 1, n is 0 or 1 and m is 2, 3 or 4; and T is a counterion or a salt forming acid, and characterized in thatb) said photographic material is developed in a hydroquinone-free developer, comprising a main developing agent of the ascorbic acid or ascorbic acid salt type, and as auxiliary developing agent a mixture of 3-pyrazolidones of which at least one has the formula (II): wherein R8 and R9 each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a group represented by the formula: (CH2)x—(L1)n1—A—(Sol) wherein x is between 0 and 5 and n1 is 0 or 1, L1 represents a divalent group selected from wherein R10=R11 or A—(Sol), R11=H, alkyl or aryl; A represents a divalent group selected from wherein q is between 0 and 5, and y is between 1 and 3; (Sol) is a solubilizing group selected from: CO2H, SO3H or a salt, SO3K, NHSO2R12, SO2NH2, SO2NHR12, polyhydroxyalkyl, wherein R12 is alkyl or aryl, R13 is OH, alkyl or aryl and R14 is hydrogen, alkyl or aryl; R3 to R7 in formula (II) each independently represent hydrogen, an alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a group represented by the formula: (X1)z—(CH2)x—(L1)n1—A—(Sol) wherein z=0 or 1; X1 represents a divalent group selected from —O—, —S—, —NR10—x, L1, n1, A, (Sol) and R10 are as defined above, with the further proviso that at least one of the radicals R3 to R9 must contain a (Sol) group.
- 2. The method according to claim 1, wherein the hydrazide nucleating agent of formula (I) is in the emulsion layer and/or in the hydrophilic colloid layer.
- 3. The method according to claim 1, wherein each Y is independently an unsubstituted phenyl group or a phenyl group substituted with an alkylthio, alkylsulfonamido, alkyl, alkoxy or trifluoromethyl group.
- 4. The method according to claim 1, wherein when X is S═O, L′ is a substituted or unsubstituted phenyl ring linked to Z via a methylene group, either directly or via a NHCO group.
- 5. The method according to claim 1, wherein when X is C, L′ is a substituted or unsubstituted alkylene group.
- 6. The method according to claim 1, wherein each Z forms independently a substituted or unsubstituted pyridyl group.
- 7. The method according to claim 1, wherein the linking group L is a substituted or unsubstituted aromatic, alkylene, polyalkylene or polyalkylene oxide group, or a substituted or unsubstituted alkylene or polyalkylene group separated by one or more heteroatoms selected from nitrogen, oxygen and sulfur, wherein the groups within L may also be separated from each others by one or more substituted or unsubstituted alkylene, polyalkylene, aryl or heterocyclic groups, and L may include, linked to each carbonyl group, a terminal oxygen atom or a group NR′, wherein R′ is a hydrogen atom or a substituted or unsubstituted alkyl group.
- 8. The method according to claim 7, wherein the linking group L is selected from —NH(CH2)2NH—, —NH(CH2)6NH—, —(CF2)2, —(CF2)3, NH(CH2)2O(CH2)2O(CH2)2O(CH2)2NH—, —OC6H4C(CH3)2C6H4O— and —NH(CH2)n-piperidino-(CH2)nNH—, where n is 0 to 4.
- 9. The method according to claim 1, wherein p and each n are and m is 2.
- 10. The method according to claim 1, wherein p is 1 and each n is 0 or 1 and m is 2, 3 or 4.
- 11. The method according to claim 1, wherein at least one of the 3-pyrazolidones of the auxiliary developing agent is 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone.
- 12. The method according to claim 1, wherein at least one of the 3-pyrazolidones of the auxiliary developing agent of formula (II) is
- 13. The method according to claim 1, wherein at least one of the 3-pyrazolidones of the auxiliary developing agent of formula (II) is
- 14. The method according to claim 1, wherein the nucleating agent of formula (I) is
- 15. The method according to claim 1, wherein the nucleating agent of formula (I) is
- 16. The method according to claim 1, wherein one of the 3-pyrazolidones of the auxiliary developing agent of formula (II) is and the nucleating agent of formula (I) is
- 17. The method according to claim 1, wherein one of the 3-pyrazolidones of the auxiliary developing agent of formula (II) is and the nucleating agent of formula (I) is
- 18. The method according to claim 1, wherein the developer comprises a development accelerator.
- 19. The method according to claim 18, wherein one of the 3-pyrazolidones of the auxiliary developing agent of formula (II) is and the nucleating agent of formula (I) is and the development accelerator is 1-phenethyl-2-picolinium bromide.
Priority Claims (1)
Number |
Date |
Country |
Kind |
02 07603 |
Jun 2002 |
FR |
|
CROSS REFERENCE TO RELATED APPLICATION
This application is cross-related to British patent application No. 0214122.4, filed Jun. 19, 2002.
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