Method of forming color images

• US 5,128,238 A
• Filed: 05/03/1990
• Issued: 07/07/1992
• Est. Priority Date: 05/23/1988
• Status: Expired due to Term

• Current Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Original Assignee: Fuji Photo Film Co Limited (Fujifilm Holdings Corporation)
• Inventors: Abe, Akira, Ueda, Shinji, Inoue, Noriyuki, Nakazyo, Kiyoshi
• Primary Examiner(s): Bowers, Jr., Charles L.
• Assistant Examiner(s): Neville, Thomas R.
• Application Number:
  US07/519,341
• Time in Patent Office: 796 Days
• Field of Search: 430/378, 430/547, 430/380, 430/409, 430/410, 430/434
• US Class Current: 430/378
• CPC Class Codes: G03C 1/48546 characterised by the nucleating/fogging agent
• CPC Class Codes: G03C 7/3022 Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• CPC Class Codes: G03C 7/407 Development processes or agents therefor G03C7/3244 takes precedence

Abstract

A method for producing color images comprising developing a negative silver halide color photographic materials and an internal latent-image type direct positive silver halide color photogaphic material, with the same developer having a pH of 9.0 to 11.5, said direct positive photographic material containing at least one compound represented by formula (N-I) as nucleating agent and at least one compound represented by (I) or (II) as magenta coupler, thereby ensuring high color reproducibility to both photographic materials: ##STR1## wherein the symbols and substituents of said formulae are as defined in the specification.

Claims

1. A method of producing color images comprising continuously developing

(1) a negative silver halide color photographic light-sensitive material, which has been subjected to image-wise exposure, and which has at least one silver halide emulsion layer on a support and contains a nondiffusible coupler capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and

(2) a direct positive silver halide color photographic light-sensitive material, which has been exposed to image-wise exposure, and which has at least one silver halide emulsion layer on a support and contains a nondiffusible coupler capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent,

with the same developer having a pH of 10.15 to 11.0,

wherein the color developer used for development is one which has been used for development of the direct positive silver halide color photographic material and the negative silver halide color photographic material in a ratio of the area of the former to the area of the latter is from 5/95 to 95/5, and which has become stable by continuous use and replenishment until the constituents of the developer have substantially achieved an equilibrium state,

wherein the bromide ion concentration in the color developer is from 1.0×

10^-2 to 2.5×

10^-2 gram ion/l,

wherein the amount of benzyl alcohol in the color developer is from 5×

10^-2 to 2×

10^-1 mol/l,

said direct positive photographic material containing i) at least one compound represented by formula (N-I), ##STR77## wherein Z¹¹ represents a nonmetallic atomic group necessary to complete a 5- or 6-membered heterocyclic ring, which may be substituted;

R¹¹ represents a unsubstituted or substituted aliphatic hydrocarbon residue;

R¹² represents a hydrogen atom, an unsubstituted or substituted aliphatic or aromatic hydrocarbon residue, or a residue forming a ring by binding to the heterocyclic ring completed by Z¹¹ ;

provided at least one of the groups R¹¹, R¹² and Z¹¹ contains a alkynyl group, an aliphatic or aromatic acyl group, a hydrazino group or a hydrazono group, or R¹¹ and R¹² combine with each other to complete a 6-membered ring as a dihydropyridinium skeleton, and at least one of the groups R¹¹, R¹² and Z¹¹ may contain a group capable of accelerating adsorption onto silver halide grains;

Y¹ represents a counter ion for maintaining charge balance; and

n represents 0 or 1, and

(ii) at least one magenta coupler selected from the group consisting of compounds represented by formula (II-2) or (II-3);

##STR78## wherein R¹¹ and R¹² each represents a hydrogen atom, a halogen atom, a cyano group, an aliphatic or aromatic hydrocarbon group, or a heterocyclic group, ##STR79## (wherein R'"'"'₁ represents a hydrogen atom, a halogen atom, a cyano group an aliphatic or aromatic hydrocarbon or heterocyclic group), a silyl group, a silyloxy group, a sililamino group, an imido group, a carbamoyl group, a sulfamoyl group, or a sulfamoylamino group, and X is an eliminatable group; and

R¹¹ and R¹² and X each may be a divalent group via which the corresponding coupler may form a dimer, or a linking group connecting the polymer chain to the mother nucleus of the corresponding coupler.

2. The method of producing color images as in claim 1, wherein said developer contains at least one compound selected from the group consisting of compounds represented by the formula (III) or formula (IV) and salts thereof:

##STR80## wherein R₁₀₁, R₁₀₂ and R₁₀₃ each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group;

R₁₀₄ represents a hydrogen atom, a hydroxyl group, a hydrazino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group;

X¹¹ represents a divalent group;

n represents 0 or 1, but when n is 0, R₁₀₄ must be an alkyl group, an aryl group or a heterocyclic group; and

further, R₁₀₃ and R₁₀₄ may form a hetero ring by combining with each other, ##STR81## wherein R¹⁰⁵ and R¹⁰⁶ each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aromatic heterocyclic group, and further they may combine with each other to form a hetero ring together with the nitrogen atom, but with the proviso that R¹⁰⁵ and R¹⁰⁶ are not simultaneously a hydrogen atom.

3. The method of producing color images as in claim 2, wherein said developer contains at least one compound selected from the group consisting of compounds represented by formula (V) or formula (VI), and salts thereof:

##STR82## wherein R⁷ represents a hydroxyalkyl group containing 2 to 6 carbon atoms;

R⁸ and R⁹ each represent a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group containing 2 to 6 carbon atoms, a benzyl group, or a group of the formula ##STR83## m represents an integer from 1 to 6;

X² and Z¹ each represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, or a hydroxyalkyl group containing 2 to 6 carbon atoms;

##STR84## wherein X³ represents a trivalent group necessary to complete a condensed ring;

R¹⁰ and R¹¹, where may be the same or different, each represents an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

4. The method of producing color images as in claim 1, wherein said direct positive photosensitive material contains at least one compound selected from the group consisting of compounds represented by formula (VII) or formula (VIII):

##STR85## wherein Q represents atoms necessary to complete a 5- or 6-membered heterocyclic ring, which may be fused together with an aromatic carbon ring or an aromatic hetero ring;

Y represents a divalent linking group comprising an atom or atomic group selected from hydrogen, carbon, nitrogen, oxygen and sulfur atoms;

R represents an organic group containing at least one thioether, amino, ammonium, ether or heterocyclic moiety;

n represents 0 or 1;

m represents 0, 1 or 2; and

M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group dissociable under alkaline conditions;

##STR86## wherein Q'"'"' represents atoms necessary to complete a 5- or 6-membered hetero ring capable of forming iminosilver;

Y, R, n and M have the same meanings as in (VII), respectively;

m represents 1 or 2.

5. The method of producing color images as in claim 1, wherein said heterocyclic ring completed by Z¹¹ in formula (N-I) is a ring selected from the group consisting of a substituted or unsubstituted quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium naphthoxazolium, and benzoxazolinium nuclei.

6. The method of producing color images as in claim 1, wherein Z¹¹ in formula (N-1) is substituted with a substituent selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an aliphatic or aromatic acyloxy group, an aliphatic or aromatic acylamino group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfonyloxy group, an aliphatic or aromatic sulfonylamino group, a carboxyl group, an aliphatic or aromatic acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carboxylate group, a hydrazino group, a hydrazono group, an imino group, said substituents may further be substituted with any of the foregoing substituents;

or said Z¹¹ is substituted with a substituent selected from the group consisting a heterocyclic quaternary ammonium group completed by Z¹¹ via an linkage selected from the group consisting of a bonding, an atom or atomic group containing at least one atom selected from among C, N, S, and O.

7. The method of producing color images as in claim 5, wherein said aliphatic hydrocarbon group represented by R¹¹ and R¹² in formula (N-I) is an unsubstituted alkyl group containing 1 to 18 carbon atoms, or a substituted alkyl group whose alkyl moiety contains 1 to 18 carbon atoms;

said aryl group represented by R¹² in formula (N-I) contains 6 to 20 carbon atoms; and

a substituent for the substituted alkyl group or a substituent with which said aryl group may be substituted is a substituent selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an aliphatic or aromatic acyloxy group, an aliphatic or aromatic acylamino group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic sulfonyloxy group, an aliphatic or aromatic sulfonylamino group, a carboxyl group, an aliphatic or aromatic acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carboxylate group, a hydrazino group, a hydrazono group, an imino group, said substituents may further be substituted with any of the foregoing substituents.

8. The method of producing color images as in claim 1, wherein Y'"'"' for charge balance in formula (N-I) is a counter ion selected from the group consisting of a bromine ion, a chlorine ion, an iodine ion, a p-toluenesulfonic acid ion, an ethylsulfonic acid ion, a perchloric acid ion, a trifluoromethanesulfonic acid ion, a thiocyanic acid ion, BF₄^-, and PF₆^-.

9. The method of producing color images as in claim 1, wherein the compound represented by formula (N-I) is incorporated in an amount of from 0.2 to 2.0 g/m².

10. The method of producing color images as in claim 2, wherein said compound is incorporated in the developer in an amount of 1×

10^-4 to 5×

10^-1 mol per liter of the developer.

11. The method of producing color images as in claim 3, wherein said compound represented by formula (V) is incorporated in an amount of 0.01 to 20 g per liter of the developer.

12. The method of producing color images as in claim 3, wherein said compound represented by formula (VI) is incorporated in an amount of 0.01 to 100 g per liter of the developer.

13. The method of producing color images as in claim 4, wherein said compound of formula (VII) and/or (VIII) is incorporated in an amount of 1×

10^-6 to 1×

10^-2 mol per mol of silver.

14. The method of producing color images as in claim 1, wherein said magenta coupler is incorporated in an amount of 0.001 to 1 mole per mole of light-sensitive silver halide.

15. The method of producing color images as in claim 1, wherein said direct positive photographic material contains at least one nucleating agent represented by formula (N-II);

##STR87## wherein R₁₅ represents an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue or a heterocyclic group;

R₁₆ represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group;

G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene ##STR88## group;

R₁₇ and R₁₈ are both a hydrogen atom, or one of them is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group or an acyl group; and

wherein G, R₁₆, and R₁₈ and the hydrazine nitrogen together may form a hydrazone structure ##STR89## said groups set forth above may be substituted.

16. The method of producing color images as in claim 15, wherein said nucleating agent represented by formula (N-I) is incorporated in an amount of 50 wt % or more of the total amount of nucleating agent.

17. The method of producing color images as in claim 4, wherein said compound represented by formula (VII) is a compound represented by formula (VII-1), (VII-2), (VII-3) or (VII-4);

##STR90## wherein M, R, Y and n have the same meaning as those in the formula (VII); and

X represents an oxygen, sulfur or selenium atom;

##STR91## wherein R'"'"' represents a hydrogen atom, a halogen atom, a nitro group, a mercapto group, an unsubstituted amino group, a substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl group, or --Y)_n R;

R" represents a hydrogen atom, unsubstituted amino, or --Y)_n R;

when both R'"'"' and R" represent --Y)_n R, they may be the same or different;

but where at least either R'"'"' or R" must represent --Y)_n R;

M, R, Y and n have the same meanings as in the formula (VII), respectively;

##STR92## wherein R'"'"'" represents --Y)_n R; and

M, R, Y and n have the same meanings as in the foregoing (VII), respectively;

##STR93## wherein R₁₁ and R₁₂ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a nitro group, or a substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl group; and

M and R'"'"'" have the same meanings as those in the formula (VII-3), respectively.

18. The method of producing color images as in claim 3, wherein said compound represented by formula (VI) is a compound represented by the formulae (VI-a) or (VI-b);

##STR94## wherein X⁴ represents ##STR95## R¹² and R¹³ are defined as R¹⁰ and R¹¹ in the formula (VI); and

R¹⁴ represents the same group as R¹⁰ and R¹¹, or --CH² CO--;

##STR96## wherein R¹⁵ and R¹⁶ have the same meaning as R¹⁰ and R¹¹ in the formula (VI).

19. The method of producing color images as in claim 1, wherein the pH of the developer is from 10.20 to 10.5.

20. The method of producing color images as in claim 1, wherein the ratio of the area is from 10/90 to 90/10.

21. The method of producing color images as in claim 1, wherein the processing temperature of the color developer is from 36°

to 50°

C.

22. The method of producing color images as in claim 1, wherein the amount of benzyl alcohol in the color developer is from 1×

10^-1 to 2×

10^-1 mol/l.

23. The method of producing color images as in claim 1, wherein the color developer is substantially free from iodide ions.

24. The method of producing color images as in claim 1, wherein the silver halide in the direct positive silver halide color photographic material is silver bromochloride or silver bromide.

25. The method of producing color images as in claim 1, wherein the bromide ion concentration in the color developer is from 1.0×

10^-2 to 2.0×

10^-2 gram ion/l.