Title: Concentrated color developer composition used for silver halide photographic sensitized material and processing method by use thereof
Abstract: A one-part photographic developing concentrate comprising: (i) a paraphenylene diamine color developing agent; and (ii) a water-soluble organic solvent, wherein a molar ratio of sodium ion to potassium ion is at least 3, and a molar ratio of sulfate ion to carbonate ion is at least 0.25.
Patent Number: 6,900,004 Issued on 05/31/2005 to Satake
| Inventors:
|
Satake; Wataru (Hino, JP)
|
| Assignee:
|
Konica Corporation (JP)
|
| Appl. No.:
|
606490 |
| Filed:
|
June 26, 2003 |
Foreign Application Priority Data
| Aug 09, 2002[JP] | 2002-232569 |
| Current U.S. Class: |
430/466; 430/486; 430/491; 430/492 |
| Intern'l Class: |
G03C 007/41.3 |
| Field of Search: |
430/466,486,491,492
|
References Cited [Referenced By]
U.S. Patent Documents
| 6413703 | Jul., 2002 | Tappe et al.
| |
| Foreign Patent Documents |
| 1293654 | Oct., 1972 | GB.
| |
| WO/02/2537/1 | Mar., 2002 | WO.
| |
Other References
European Search Report EP 03 25 4880.
|
Primary Examiner: Le; Hoa Van
Attorney, Agent or Firm: Muserlian, Lucas and Mercanti
Claims
1. A one-part photographic developing concentrate comprising:
(i) a paraphenylene diamine color developing agent;
(ii) a water-soluble organic solvent; and
(iii) sodium ions, potassium ions, sulfate ions and carbonate ions,
wherein a molar ratio of sodium ion to potassium ion is at least 3, and a molar
ratio of sulfate ion to carbonate ion is at least 0.25.
2. The one-part photographic developing concentrate of claim 1, wherein a compound
represented by Formulas (A-I) to (A-IV) is further contained:
##STR24##
wherein A
11, A
12, A
13 and A
14, which
may be the same or different, each represents —CH
2OH, —PO
3(M
6)
or —COOM
7; M
6 and M
7 each represents a
hydrogen atom, an ammonium group, an alkaline metal atom or an organic ammonium
group; X represents an alkylene group having 2 to 6 carbon atoms or —(B-
1O)
n—B
2—;
n represents an integer of 1 to 6; and B
1 and B
2, which may
be the same or different, each represents an alkylene group having 1 to 5 carbon
atoms,
##STR25##
wherein A
21, A
22, A
23 and A
24, which
may be the same or different, each represents —CH
2OH, —COOM
1
or —PO
3(M
2)
2; M
1 and M
2
each represents a hydrogen atom, an ammonium group, an alkaline metal or
an organic ammonium group; X
1 represents a straight or branched alkylene
group having 2 to 6 carbon atoms, a saturated or unsaturated organic group which
forms a ring, or —(B
11O)
n5—B
12—;
n5 represents an integer of 1-6; B
11 and B
12, which may be
the same or different, each represents an alkylene group having 1-5 carbon atoms;
and n1, n2, n3 and n4, which may be the same or different, each represents an integer
of not less than 1 and at least one of n1, n2, n3 and n4 is 2 or more,
##STR26##
wherein A
1, A
2, A
3 and A
4, which
may be the same or different, each represents a hydrogen atom, a hydroxyl group,
—COOM
3, —PO
3(M
4)
2, —CH
2COOM
5,
—CH
2OH or a lower alkyl group, however, at least one of A
1
to A
4 represents —COOM
3, —PO
3(M
4)
2,
or —COOM
5; M
1, M
2, M
3, M
4,
and M
5 each represents a hydrogen atom, an ammonium group, an alkaline
metal atom or an organic ammonium group; and n7 represents an integer of 0 to 2,
##STR27##
wherein, A
5, A
6, A
7, A
8 and A
9,
which may be the same or different, each represents —COOM
3 or
—PO
3M
4M
5; M
3, M
4 and
M5, which may be the same or different, each represents a hydrogen atom or an alkaline
metal atom; and n represents an integer of 1 or 2.
3. The one-part photographic developing concentrate of claim 1, wherein the developing
concentrate does not comprise a fluorescent whitening agent.
4. A one-part photographic developing concentrate comprising:
(i) a paraphenylene diamine color developing agent; and
(ii) a water-soluble organic solvent,
wherein a molar ratio of sodium ion to potassium ion is at least 3, and a molar
ratio of sulfate ion to carbonate ion is at least 0.25; and
wherein a compound represented by formulas (A-I) to (A-IV) is further contained:
##STR28##
wherein A
11, A
12, A
13 and A
14, which
may be the same or different , each represents —CH
2OH, —PO
3(M
6)
or —COOM
7; M
6 and M
7 each represents a
hydrogen atom, an ammonium group, an alkaline metal atom or an organic ammonium
group; X represents an alkylene group having 2 to 6 carbon atoms or —(B
1O)
n—B
2—;
n represents an integer of 1 to 6; and B
1 and B
2, which may
be the same or different , each represents an alkylene group having 1 to 5 carbon
atoms,
##STR29##
wherein A
21, A
22, A
23 and A
24, which
may be the same or different, each represents —CH
2OH, —COOM
1
or —PO
3(M
2)
2; M
1 and M
2
each represents a hydrogen atom, an ammonium group, an alkaline metal or
an organic ammonium group; X
1 represents a straight or branched alkylene
group having 2 to 6 carbon atoms, a saturated or unsaturated organic group which
forms a ring, or —(B
11O)
n5—B
12—;
n5 represents an integer of 1-6; B
11 and B
12, which may be
the same or different, each represents an alkylene group having 1-5 carbon atoms;
and n1, n2, n3 and n4, which may be the same or different, each represents an integer
of not less than 1 and at least one of n1, n2, n3 and n4 is 2 or more,
##STR30##
wherein A
1, A
2, A
3 and A
4, which
may be the same or different, each represents a hydrogen atom, a hydroxyl group,
—COOM
3, —PO
3(M
4)
2, —CH
2COOM
5,
—CH
2OH or a lower alkyl group, however, at least one of A
1
to A
4 represents —COOM
3, —PO
3(M
4)
2,
or —COOM
5; M
1, M
2, M
3, M
4,
and M
5 each represents a hydrogen atom, an ammonium group, an alkaline
metal atom or an organic ammonium group; and n7 represents an integer of 0 to 2,
##STR31##
wherein, A
5, A
6, A
7, A
8 and A
9,
which may be the same or different, each represents —COOM
3 or
—PO
3M
4M
5; M
3, M
4 and
M
5, which may be the same or different, each represents a hydrogen atom
or an alkaline metal atom; and n represents an integer of 1 or 2.
5. The one-part photographic developing concentrate of claim 1, wherein the developing
concentrate does not comprise any other cations than sodium ion.
6. The one-part photographic developing concentrate of claim 1, wherein the developing
concentrate does not comprise a fluorescent whitening agent.
Description
TECHNICAL FIELD
The present invention relates to a concentrated color developer composition used
for silver halide photographic materials (hereinafter, also denoted simply as photographic
sensitized materials or simpler still as photographic materials) and a processing
method by use thereof, and in particular, to a concentrated color developer composition
exhibiting improved fluctuation of oxidation-reduction potential even after storage
at relatively high temperature, leading to superior developing performance of continuous
processing developing reduction capability, that is, reduced variation in gamma
balance even when used as a replenisher after storage, and a processing method
by use thereof.
BACKGROUND
Photographic color developer compositions are used for processing color
photographic film or paper to produce desired images. In general, such a composition
contains a color developing agent as a reducing agent, for example, 4-amino-3-methyl-N-(2-methanesulfonamidoethyl)aniline,
forming a desired dye upon reaction with a dye forming coupler. U.S. Pat. Nos.
4,892,804, 4,876,174, 5,354,646 and 5,660,974 describe such various color developer compositions.
Generally, to replenish processing components which have been consumed
in reaction or carried out by processed photographic material, a color developer
replenishing solution is supplied to a color developing solution in a color developing
tank. Such replenishment is designed to maintain a prescribed developing capability
and stability of the color developing agent.
A color developer replenishing solution is supplied in the form of at least three
separated components (or concentrated compositions), which are usually mixed immediately
before use. Separated plural parts are often supplied to maintain chemical reactivity
and solubility of ingredients. Stocking these together in solution under alkaline
conditions results in deterioration or reaction with each other. The components
comprise one containing a color developing agent, another one containing material
to maintain alkalinity and one containing a compound such as an anti-oxidizing
agent. A homogeneous color developing solution can usually be obtained by mixing
all of these components with water.
In the photographic industry, reducing the number of such components used for
preparation of the replenishing solution has been desired to reduce bothersome
handling. Solutions ready to use as such, so-called ready-to-use type solutions,
a concentrated composition or a powdery mixture has been commercially available
in this field of technology. For example, EP-A No. 0793141 (hereinafter, the term
EP-A refers to European Patent Application Publication) describes a color developer
composition comprised of two components, which can be supplied in solid or liquid form.
In these ready-to-use type solutions, which are superior in ease of use, all
of
the ingredients are prepared in specific concentrations in which a large amount
of water is contained, resulting in increased cost of manufacture, transport and storage.
In the photographic industry, therefore, it has been and still is desired to
provide
a photographic processing composition in a concentrated form (including a color
developer composition) so that a manufacturer or consumer can enjoy reduced cost
for transport or storage of basically a large amount of water, thereby rendering
smaller containers effective. Further desired in the photographic industry is a
composition which is usable immediately after removing it from the container (for
example, known as an automatically replenishing processor), without the need of
mixing various ingredients (thereby reducing errors in mixing).
When comparing a liquid concentrate with a solid mixture (e.g., powder, tablet),
the liquid concentrate is more convenient to use but is more expensive for packaging.
Although powder can be highly concentrated, it is difficult to supply stable powder
for respective photographic chemical compositions. Further, powder has problems
such as creating dust, and the necessity of separately packaging and complicated
operations for measuring and mixing. Further, it takes a lot of effort and time
to complete dissolution into a uniform solution.
Another concentration form known in the art is a paste or slurry of chemicals,
as described in EP-A Nos. 0204372 and 0800111. However, such a mixture has defects
in that it exhibit insufficient uniformity and retarded dissolution of its solid components.
Recently, to overcome the foregoing problems, a single component type color
developer composition (a single mixture) has become commercially available. However,
precipitates (such as slurry) or plural solvent phases exist in such a composition,
making it necessary to conduct sufficient stirring or mixing prior to use.
Accordingly, strongly desired has been a single component type color
developer composition (a single mixture) which is concentrated homogeneously and
stably. Such a concentrated composition not only reduces costs to transport a solution
diluted with a large amount of water and to stock the solution, but it also eliminates
the necessity to mix plural parts or stir plural phase compositions to, providing
a product desired by consumers.
Specifically CD-3 (4-amino-3-methyl-N-(2-methanesulfonamidoethyl)aniline,
which is used for a color developing agent of color paper, exhibits low solubility,
leading to the assumption that forming a single component is difficult. To solve
these problems, proposed are methods such as using CD-3 free amine described in
JP-B 3-150131 (hereinafter, the term JP-B refers to Examined Japanese Patent Publication),
and prescribing a molar ratio of a Na salt and a K salt described in WO 02/25371.
Employing these methods, it becomes possible to provide a single component kit
(or called as one-part photographic developing concentrate) with an improved low
temperature deposition, resulting in no precipitates.
However, in a single solution kit, fluctuation of development processing
levels in long term storage can be taken for granted in addition to the foregoing
low temperature deposition. This is inferred from oxidation-reduction level fluctuation
of the solution after storage, and consequently, is encountered for the first time
with a single solution kit in which all of the components are contained in one solution.
The fluctuation of the oxidation-reduction potential is not caused by deterioration
(oxidizing degradation) of CD-3, but generated even if the required CD-3 concentration exists.
Employing the foregoing prior art, these problems cannot be overcome. In
cases when the fluctuation of the development processing level is generated over
a long term storage, adjustment of the setting condition of an automated processing
apparatus for development processing is mandatory, resulting in increased frequency
of adjusting operations.
Specifically, in recent year the required quality of processing solution
stability has become problematic due to low replenishing rate, rapid processing
and enhanced processing capability for digital exposures of the processing solution.
On the other hand, the processing volume per shop is decreasing because of an increase
in the number of minilab shops. Therefore, the storage period of the chemicals
tends to be excessively long from the production to usage.
For this reason, it is required to promptly provide the technology to overcome
these problems.
SUMMARY
Accordingly, an object of this invention is to provide a concentrated
color developer composition exhibiting reduced variation in oxidation-reduction
potential even after storage at relatively high temperature, thereby effectively
inhibiting variation in gamma balance before and after storage, and a processing
method by use thereof.
The foregoing problem can be solved by the following constitution:
1. A one-part photographic developing concentrate comprising:
- (i) a para(p-)phenylene diamine color developing agent; and
- (ii) a water-soluble organic solvent,
- wherein a molar ratio of sodium ion to potassium ion is at least 3,
and a molar ratio of sulfate ion to carbonate ion is at least 0.25.
2. The one-part photographic developing concentrate of item 1, wherein the
developing concentrate does not comprise any other cations than sodium ion.
3. The one-part photographic developing concentrate of item 1 or 2, wherein
a compound represented by Formulas (A-I) to (A-IV) is further contained:
##STR1##
- wherein A11, A12, A13 and A14,
which may be the same or different, each represents —CH2OH, —PO3(M6)
or —COOM7; M6 and M7 each represents a
hydrogen atom, an ammonium group, an alkaline metal atom or an organic ammonium
group; X represents an alkylene group having 2 to 6 carbon atoms or —(B1O)n—B2—;
n represents an integer of 1 to 6; and B1 and B2, which may
be the same or different, each represents an alkylene group having 1 to 5 carbon
atoms.
##STR2##
- wherein A21, A22, A23 and A24,
which may be the same or different, each represents —CH2OH, —COOM1
or —PO3(M2)2; M1 and M2
each represents a hydrogen atom, an ammonium group, an alkaline metal or
an organic ammonium group; X1 represents a straight or branched alkylene
group having 2 to 6 carbon atoms, a saturated or unsaturated organic group which
forms a ring, or —(B11O)n5—B12—;
n5 represents an integer of 1-6; B11 and B12, which may be
the same or different, each represents an alkylene group having 1-5 carbon atoms;
and n1, n2, n3 and n4, which may be the same or different, each represents an integer
of not less than 1 and at least one of n1, n2, n3 and n4 is 2 or more.
##STR3##
- wherein A1, A2, A3 and A4,
which may be the same or different, each represents a hydrogen atom, a hydroxyl
group, —COOM3, —PO3(M4)2,
—CH2COOM5, —CH2OH or a lower alkyl
group, however, at least one of A1 to A4 represents —COOM3,
—PO3(M4)2, or —COOM5;
M1, M2, M3, M4, and M5 each
represents a hydrogen atom, an ammonium group, an alkaline metal atom or an organic
ammonium group; and n7 represents an integer of 0 to 2.
##STR4##
- wherein, A5, A6, A7, A8
and A9, which may be the same or different, each represents —COOM3
or —PO3M4M5; M3, M4
and M5, which may be the same or different, each represents a
hydrogen atom or an alkaline metal atom; and n represents an integer of 1 or 2.
4. The one-part photographic developing concentrate of any one of items
1 to 3, wherein the developing concentrate does not substantially comprise a fluorescent
whitening agent.
5. A method for processing a silver halide color photographic material,
comprising the steps of:
- imagewise irradiating the photographic material;
- developing the irradiated photographic material in a developing solution
which is prepared by diluting a volume of the developing concentrate of any one
of items 1 to 4 with water having a volume of at least 3 times of the volume of
the developing concentrate; and then
- desilvering the developed photographic material.
6. The method for processing a silver halide color photographic material
of item 5, wherein the developing solution is prepared by diluting the developing
concentrate which does not comprise any other cations than sodium ion.
7. The method for processing a silver halide color photographic material
of item 5 or 6, wherein the developing solution is prepared by diluting the developing
concentrate of item 3.
8. The method for processing a silver halide color photographic material
of any one of item 5 to 7, wherein the developing solution is prepared by diluting
the developing concentrate of item 4.
A concentrated color developer composition in the form of a single component,
prepared
in accordance with the prior art exhibited marked variation in oxidation-reduction
potential after storage, adversely affecting developability, specifically gamma
balance, resulting in major practical problems. The above-described problem was
overcome by the foregoing constitution according to this invention.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 represents a simplified block diagram of a printer-processor which was
combined with an automated processing apparatus and a photographic printer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be detailed below. Specific examples of preferred
p-phenylenediamine type color developing agents usable in the color developer composition
of the present invention are shown below, but color developing agents usable in
this invention are not limited to these examples.
Exemplified Compounds
- 1. N,N-diethyl-p-phenylenediamine
- 2. 2-amino-5-diethylaminotoluene
- 3. 2-amino-5-(N-ethyl-N-laurylamino)toluene
- 4. 4-(N-ethyl-N-(β-hydroxyethyl)amino)aniline
- 5. 2-methyl-4-(N-ethyl-N-(β-hydroxyethyl)amino)aniline
- 6. 4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamide)ethyl)aniline
- 7. N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide
- 8. N,N-dimethyl-p-phenylenediamine
- 9. 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline
- 10. 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline
Of these p-phenylenediamine derivatives, specifically preferably used compounds
in this invention are 4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamide)ethyl)aniline
(exemplified compound 6) and 2-methyl-4-(N-ethyl-N-(β-hydroxyethyl)amino)aniline
(exemplified compound 5).
Further, these p-phenyleneamine derivatives are used in the form of a sulfate,
hydrochloride, sulfite or p-toluenesulfonate. Considering the concentrated composition,
the added amount of p-phenylenediamine type color developing agents in this invention
is preferably at least 0.08 mol/L, and more preferably at least 0.1 mol/L.
Examples of water soluble solvents suitable to the concentrated color developing
composition of this invention include carboxylic acid amides and urea derivatives
such as dimethylformamide, methylacetamide, dimethylacetamide, N,N′-dimethylurea,
tetramethylurea, methanesulfonamide, dimethylethyleneurea, N-acetylglycine, N-valeramide,
isovaleramide, N-butylamide, N,N-dimethylbutylamide, N-(2-hydroxyphenyl)acetamide,
N-(2-methoxyphenyl)acetamide, 2-pyrrolidinone, ε-caplolactam, acetanilide,
benzamide, toluenesulfonamide, and phthalimide; aliphatic and cyclic alcohols such
as isopropanol, tert.-butyl alcohol, cyclohexanol, cyclohexane methanol, and 1,4-cyclohexane
dimethanol; aliphatic and cyclic polyalcohols such as glycols, poluglycols, polywaxes,
trimethyl-1,6-hexanediol, glycerol, 1,1,1-trimethylolpropane, pentaerythrite, and
sorbitol; aliphatic and cyclic ketones such as acetone, ethyl methyl ketone, diethyl
ketone, tert.-butyl methyl ketone, diisobutyl ketone, acetylacetone, acetonylacetone,
cyclopentanone, ans acetophenol; aliphatic and cyclic carboxylates such as trimethoxymethane,
methyl acetate, aryl acetate, ethylene acetate glycol monomethyl ether, ethylene
glycol diacetate, 1-glycerol acetate, glycerol acetate, methylcyclohexyl acetate,
methyl salicylate, and phenyl salicylate; aliphatic and cyclic phosphonates such
as dimethyl methylphosphonate, and diethyl allylphosphonate; aliphatic and cyclic
oxyalcohols such as 4-hydroxy-4-methyl-2-pentanone, and salicylaldehyde; aliphatic
and cyclic aldehydes such as acetaldehyde, propanal, trimethylacetaldehyde, crotonaldehyde,
glutaraldehyde, 1,2,5,6-tetrahydrobenzaldehyde, benzaldehyde, benzenepropane, and
terephthalaldehyde; aliphatic and cyclic oximes such as butanone oxime, and cyclohexanone
oxime; aliphatic and cyclic amines (primary, secondary or tertiary), such as ethylamine,
diethylamine, triethylamine, dipropylamine, pyrrolidine, morpholine, and 2-amino-pyrimidine;
aliphatic and cyclic polyamines (primary, secondary or tertiary), such as ethylenediamine,
1-amino-2-diethylaminoethane, methyl-bis(2-methylaminoethyl)-amine, permethyldiethylenetriamine,
1,4-cyclohexanediamine, and 1,4-benzenediamine; aliphatic and cyclic hydroxyamines
such as ethanolamine, 2-methylethylamine, 2-methylaminoethanol, 2-(dimethylamino)ethanol,
2-(2-dimethylaminoethoxy)-ethanol, diethanolamine, N-methyldiethanolamine, triethanolamine,
2-(2-aminoethylamino)ethanol, triisopropanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol,
3-propanediol, 1-piperidineethanol, 2-aminophenol, barbituric acid, 2-(4-aminophenoxy)-ethanol,
and 5-amino-1-naphthol.
With regard to the constitution of the concentrated color developing composition
for a silver halide color photographic sensitized material of this invention, the
molar ratio of (Na ions)/(K ions) used therein is necessarily larger than 3. In
cases when K ions exceed Na ions, stability of the color developing agent in the
solution deteriorates, resulting in an increased tendency to generate fluctuation
of the oxidation-reduction potential.
In the present invention, it has been confirmed that stability is enhanced by
adjusting the ratio of Na ions/K ions within the foregoing range. A more preferable
range is obtained in the system which uses no K ions (all of the cations being
Na ions, that is, Na ions are 100%). The ratio of Na ions/K ions is necessarily
in the foregoing range, however, other cations may exist.
With regard to the constitution of the concentrated color developing composition
for a silver halide color photographic sensitized material of this invention, the
molar ratio of carbonate ions/sulfates ion used therein is necessarily more than
0.25. Generally, as knowledge regarding stability of a concentrated color developing
composition, one about variation of cations is well known. However, the inventors
of this invention have repeated experiments about an anion ratio to find a balance
to enhance the foregoing storage stability.
The more preferable range of the molar ratio of carbonate ions/sulfate ions used
in the invention is at least 0.30.
The compounds represented by Formulas (A-I) through (A-IV), which are used in
the concentrated color developing composition of this invention, will now be described.
Initially, the compounds represented by Formula (A-I) will be described.
In the Formula, A
11-A
14, which may be the same or different,
each represents —CH
2OH, —PO
3(M
6)
2
or —COOM
7. M
6 and M
7 each represents a
hydrogen atom, an ammonium group, an alkaline metal atom (such as a sodium and
potassium), or an organic ammonium group (such as a methylammonium group and a
trimethylammonium group). X represents an alkylene group having 2-6 carbon atoms,
which may be substituted, or —(B
1O)n—B
2—.
Further, B
1 and B
2, which may be the same or different, each
represents an alkylene group having 1-5 carbon atoms, which may be substituted.
Examples of alkylene groups represented by X include ethylene, trimethylene and
tetramethylene. Further, examples of alkylene group represented by B
1 and
B
2 include methylene, ethylene and trimethylene. Examples of substituents
of alkylene groups represented by X, B
1 or B
2 include a hydroxyl
group, and an alkyl group having 1-3 carbon atoms (such as methyl group and ethyl
group). "n" represents an integer of 1-6, and preferably 1-4.
Specific examples of preferred compounds represented by Formula (A-I) are
shown below but compounds usable in the invention are not limited to these.
##STR5##
##STR6##
The compounds represented by foregoing Formula (A-I) can be synthesized based
on commonly known methods.
Of these, specifically preferable compounds are (A-I-1), (A-I-3) and (A-I-14).
The compounds represented by Formula (A-II) will be described below.
In the Formula, A
21-A
24, which may be the same or different,
each represents —CH
2OH, —PO
3(M
2)
2
or —COOM
1. M
1 and M
2 represent an hydrogen
atom, an ammonium group, an alkaline metal atom (such as sodium and potassium),
or an organic ammonium group (such as a methylammonium group and a trimethylammonium group).
X
1 represents a straight or branched chained alkylene group
having 2-6 carbon atoms, a saturated or unsaturated organic group forming a ring,
or —(B
11O)n
5B
12—. B
11 and
B
12, which may be the same or different, each represents an alkylene
group having 1-5 carbon atoms (including a substitution product). "n
1"-"n
4",
which may be the same or different, represent an integer of more than 1, and at
least one of them is to be more than 2. Specific examples of alkylene groups represented
by X
1 include ethylene, trimethylene and tetramethylene. Specific examples
of alkylene groups represented by B
11 and B
12 include methylene,
ethylene and trimethylene. Examples of substituents of alkylene groups represented
by X
1, B
11 and B
12 include a hydroxyl group, an
alkyl group having 1-3 carbon atoms (such as a methyl group and an ethyl group).
"n
5" represents an integer of 1-6, preferably 1-4, and more specifically
preferably 1-2.
Specific examples of preferred compounds represented by Formula (A-II) are
shown below, but compounds usable in this invention are not limited to these.
##STR7##
##STR8##
##STR9##
##STR10##
Foregoing (A-II-16), (A-II-17), (A-II-18), (A-II-19) and (A-II-20) include
both cis isomers.
The compounds represented by foregoing Formula (A-II) can be synthesized based
on commonly known methods.
Of specific examples, specifically preferred compounds are (A-II-1), (A-II-2)
and (A-II-6).
The added amount of the compounds represented by foregoing (A-I) and (A-II) is
preferably in the range of 0.001-0.1 mol/L, and more preferably in the range of
0.005-0.05, in cases when the component is used for a color developing replenisher
as a solution diluted by a factor of 4.
Next, the compounds represented by foregoing Formula (A-III) will be described.
In Formula (A-III), A
1, A
2, A
3 and A
4,
which may be the same or different, each represents an hydrogen atom, an hydroxyl
group, —COOM
3, —PO
3(M
4)
2,
—CH
2COOM
5, —CH
2OH and a lower alkyl
group (methyl group, ethyl group, isopropyl group and n-propyl group). However,
at least one of A
1, A
2, A
3 and A
4 represents
—COOM
3, —PO
3(M
4)
2 or
—CH
2COOM
5. M
1, M
2, M
3,
M
4 and M
5 each represents an hydrogen atom, a sodium atom,
a potassium atom, a lithium atom, an ammonium atom, an alkaline metal atom, or
an organic ammonium group, and preferably a hydrogen atom, a sodium atom, or a
potassium atom. "n
7" represents an integer of 0-2.
Specific examples of preferred compounds represented by Formula (A-III)
are shown below.
##STR11##
##STR12##
The compounds represented by foregoing Formula (A-III) can be synthesized in
employing commonly known methods, such as described in JP-A 63-267750, 63-267751,
2-115172 and 2-295954 (hereinafter the term JP-A refers to unexamined Japanese
Patent Application Publication).
In cases when the concentrated color developer composition of the invention is
diluted at least 4 times as a color developer replenisher, the content of the compound
represented by formula (A-III) is preferably 0.001 to 0.1 mol/L, and more preferably
0.005 to 0.05 mol/L.
Specific examples of the compound represented by formula (A-IV) include
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic cid, diethylenetriaminepentamethylenephosphonic
acid and triethylenetetraminehexamethylenephosphonic acid, and their salts (e.g.,
alkali metal salts such as potassium, sodium and lithium). These compounds are
also commercially available.
Of these compounds represented by Formula (A-IV), diethylenetriaminepentaacetic
acid and its salt are specifically preferably employed to achieve the object of
this invention.
The processing chemical component of this invention may contain a small amount
of sulfite ions or may substantially not contain any, depending on the kind of
the targeted photographic materials. On the other hand, since, sulfite ions exhibit
significant preserving action, on the other hand, they may undesirably affect photographic
characteristics during color development processing depending on the targeted photographic
materials. In this invention, it is preferred to add a hydroxylamine derivative
or its salt. The preferred hydroxylamine derivatives are alkylhydroxylamines which
have 1-8 alkyl groups having 2-4 carbon atoms and alkylhydroxylamines which have
1-2 alkyl groups having 2-4 carbon atoms and substituted by a carboxyl group, a
sulfo group, a phosphono group, or a hydroxyl group. Employing these compounds
makes it possible to further enhance storage stability, resulting in an expanded
tolerance of air transmission rate of a container. Consequently, the tolerance
level is increased by reducing thickness of the container wall or enlarging the
specific surface. Further, in addition to the foregoing hydroxylamine derivatives,
added may be the hydroxylamines described in JP-A 1-97953, 1-186939, 1-186940 and 1-187557.
The concentrated color developer composition of this invention may contain an
inorganic preserving agent or an organic preserving agent, in addition to the foregoing
sulfite ions and hydroxylamine derivatives. An organic preserving agent indicates
all of the organic compounds which decrease the deterioration rate of aromatic
primary amine color developing agents by incorporating them into the processing
solution for photographic materials, that is, those are the organic compounds which
have a function to prevent the air oxidation of the color developing agents. Of
these, specifically effective preserving agents are hydroxylamine derivatives besides
the foregoing ones, hydroxamic acids, hydrazides, phenols, α-hydroxy ketones,
α-amino ketones, saccarides, monoamines, diamines, polyamines, quaternary
ammonium salts, nitroxy radicals, alcohols, oximes, diamido compounds and condensed
ring amines. These are disclosed in publications and specifications such as JP-A
63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63-58346,
63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat. Nos. 3,615,503, 2,494,903, JP-A
52-143020 and JP-B 48-30496 (hereinafter, the term JP-B refers to examined Japanese
Patent Publication).
pH of the concentrated color developer composition of this invention is controlled
to provide a higher pH to contain the color developing agent at a higher concentration,
usually being in the range of 11.0-13.5, preferably 12.0-13.5, and more preferably
12.5-13.5. The color developing solution and color developing replenisher are preferably
used at a pH of more than 9.5, and more preferably in the range of 10.0-12.5. To
maintain a stable pH, it is preferable to employ various buffer agents. Examples
thereof include carbonates, phosphates, borates, tetraborates, hydroxybenzoates,
glycylates, N,N-dimethylglycinates, leucinates, norleucinates, guaninates, 3,4-dihydroxyphenylalaninates,
alaninates, aminobutylates, 2-amino-2-methyl-1,3-propanediolates, valinates, prolinates,
trishydroxyaminomathanates, and lysinates. Specifically, carbonates, phosphates,
tetraborates and hydrxybenzoates superior are in a buffer capacity at a high pH,
at more than 9.0, exhibit no undesirable affects (such as fogging) to the photographic
characteristics by adding to the color developing solution, and further exhibit
the advantage of a lower cost. It is preferred to use these buffer agents to conform
to the specific gravity limits of this invention.
Specific examples of these buffer agents include sodium carbonate, potassium
carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium
phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium
borate, sodium tetraborate (borax), potassium tetraborate, o-sodium hydroxybenzoate
(sodium salicylate), o-potassium hydroxybenzoate, 5-sulfo-2-sodium hydroxybenzoate
(5-potassium sulfosalicylate), and 5-sulfo-2-hydroxybenzoate (5-potassium sulfosalicylate).
However, the present invention is not limited to these compounds. The specifically
preferable buffer agent is potassium carbonate because of the advantageous point
of the possibility of an effective increase of specific gravity without deposition
due to high solubility. The amount of buffer agents is added to the composition
so that the concentration in the diluted and prepared color developing replenisher
is at least 0.01 mol/L, and specifically 0.1-0.5 mol/L.
Generally, known is to use stilbene type fluorescent brightening agents
with the concentrated color developer composition. However, as a preferable embodiment
of this invention, it is preferred that these fluorescent brightening agents are
substantially not added. The addition of the fluorescent brightening agents is
effective to maintain the low density of the unexposed portion, which is a silver
halide photographic sensitized material for direct observation, however, it is
not preferable from the point of view of stability in the concentrated composition.
Specifically, the effect of fluctuation of oxidation-reduction potential is confirmed
in storage of a relatively long term at a high temperature condition while coexistence
with a color developing agent.
In addition to the foregoing, hydroxides of alkaline metals may be contained,
from a pH adjustment point of view.
The concentrated color developer composition of this invention has practicability
such that it provides color development to an image exposed photographic material
comprising on a support at least one silver halide emulsion layer containing imagewise
distributed developable silver halide grains. Various photographic elements containing
various types of emulsions (e.g., color negative film, color reversal film, color
movie film and print paper) can be processed using the concentrated color developer
composition of this invention. Such emulsions are commonly known in the photographic
art (as described in Research Disclosures).
Color development of an image exposed photographic material is carried out
by bringing the photographic material into contact with color developing solution
prepared according to this invention in an appropriate processing apparatus under
optimal time and temperature conditions, obtaining desired developed images. Thereafter,
additional processing can be conducted in the specific order known in the art employing
at least one of the conventional processing steps such as a development stop step,
a bleaching step, a fixing step, a bleach/fixing step, a washing (or rinsing) step,
a stabilizing step and a drying step (but not limited to these). Commonly known
are useful processing steps of various processing protocols including process C-41
for color negative film, process RA-4 for color paper and process E-6 for color
reversal film, and other useful conditions and material thereof.
The processing time and temperature in each of the respective processing steps
are known in the art. For example, color development is generally carried out at
a temperature of 20-60° C., while the preferable time of color development
is 15-250 sec. The concentrated color developer composition of this invention is
appropriately diluted at least by a factor of 4 and at most a factor of 12 to prepare
a working solution or a replenishing solution. The dilution rate is preferably
a factor of 4-10, and water is preferably used as a diluent. Dilution may be conducted
before or during processing.
EXAMPLES
Examples of this invention will be described below, but the embodiments
of this invention are not limited to these examples.
Example 1
| Concentrated Color Developer Composition |
| |
| Color developing agent (CD-3) |
the amount described in Table 1 |
| Potassium sulfite |
2 |
g |
| Diethylhydroxylamine |
25 |
g |
| Stilbene type fluorescent whitening |
6 |
g |
| agent |
| EDTA.4H |
0.04 |
mol |
| Diethylene glycol |
100 |
g |
| Potassium/sodium carbonate |
0.80 |
mol |
| Potassium/sodium sulfate |
the amount described in Table 1 |
In the above composition, the ratios of sodium/potassium and sulfate/carbonate
were adjusted to the amounts described in Table 1.
pH was adjusted to 12.5 with KOH and NaOH, after which water was added to a total
volume of 1,000 ml.
Stilbene type fluorescent brightening agent was employed, as described below.
##STR13##
This concentrated color developer composition was placed in a sealed container
and stored in an incubator for 4 months at 50° C. The foregoing concentrated
color developer compositions before and after storage were diluted by a factor
of 8 times, and the following additives were added to prepare color developing
working solutions.
| |
Potassium chloride |
5.0 |
g/L |
| |
Potassium carbonate |
4.0 |
g/L |
| |
Potassium bicarbonate |
8.0 |
g/L |
| |
pH |
10.15 |
| |
The pH was adjusted employing 50% sulfuric acid or potassium hydroxide.
The thus prepared working solutions were each measured with respect to oxidation-reduction
potential or redox potential (also denoted as E), using HM-30S (available from
TOA Electronics Ltd.) to determine the difference in E before and after storage
(ΔE=E before storage minus E after storage). Variation of oxidation-reduction
potential was determined using the following equation. The less variation of oxidation-reduction
potential indicates that a kit is superior in storage stability.
Oxidation-reduction potential variation (ΔE %)=(potential
after storage/potential before storage-1)×100. Further, development was conducted
under the following conditions, in which photographic material exposed through
an optical wedge (Konica Color QA Paper) was used to determine gamma balance as
defined below. Low variation of gamma balance indicates low variation in processing
level after storage and superior storage stability.
Gamma of each color density=Exposure amount corresponding to density 1.8 minus
exposure amount corresponding to density 0.8.
- Gamma balance=Red density gamma/Green density gamma
- Gamma balance change rate (%)=(gamma balance after storage/gamma balance
before storage-1)×100
Processing Condition
| |
| |
|
Processing |
Processing |
| |
Step |
Time |
Temperature |
| |
| |
Color developing |
45 sec. |
37.5° C. |
| |
Bleach-fixing |
45 sec. |
37.0° C. |
| |
Stabilizing |
30 sec. × 3 tanks |
37.0° C. |
| |
Drying |
60 sec. |
65° C. |
| |
The bleach-fixing solution was prepared with a usual dissolution method using
Bleach-fix Replenisher for Konica Color QA Paper K-20P2R-03 (a product of Konica Corp.).
The stabilizing solution was prepared with a usual dissolving method using Super
Stabilizer Replenisher for Konica Color QA Paper K-P3R-01 (produced by Konica Corp.).
| |
|
|
|
|
|
Gamma |
|
| |
Na:K |
CD-3 |
K2SO4 |
SO4/CO3 |
|
balance |
| |
Molar |
Amount |
Amount |
Molar |
ΔE |
change |
| No. |
ratio |
(mol) |
(mol) |
ratio |
variation |
rate (%) |
Remarks |
| 1 |
4:1 |
0.092 |
0 |
0.17 |
11.1 |
15.4 |
Comp. |
| 2 |
4:1 |
0.092 |
0.03 |
0.20 |
10.9 |
14.9 |
Comp. |
| 3 |
4:1 |
0.092 |
0.06 |
0.23 |
10.8 |
14.7 |
Comp. |
| 4 |
4:1 |
0.092 |
0.08 |
0.25 |
8.8 |
8.9 |
Inv. |
| 5 |
4:1 |
0.092 |
0.13 |
0.30 |
8.5 |
9.1 |
Inv. |
| 6 |
4:1 |
0.092 |
0.33 |
0.80 |
9.0 |
8.4 |
Inv. |
| 7 |
4:1 |
0.092 |
0.83 |
1.00 |
9.2 |
9.8 |
Inv. |
| 8 |
1:1 |
0.092 |
0.13 |
0.30 |
12.4 |
16.1 |
Comp. |
| 9 |
2:1 |
0.092 |
0.13 |
0.30 |
13.1 |
16.0 |
Comp. |
| 10 |
3:1 |
0.092 |
0.13 |
0.30 |
9.6 |
9.7 |
Inv. |
| 11 |
5:1 |
0.092 |
0.13 |
0.30 |
8.4 |
9.0 |
Inv. |
| 12 |
10:1 |
0.092 |
0.13 |
0.30 |
8.1 |
8.9 |
Inv. |
| 13 |
100:0 |
0.092 |
0.13 |
0.30 |
7.3 |
7.4 |
Inv. |
| 14 |
4:1 |
0.138 |
0 |
0.26 |
8.5 |
8.9 |
Inv. |
| Comp.: Comparative example |
| Inv.: Present invention |
As is apparent from Table 1, it was proved that the combination according to
the
invention provided a concentrated color developer composition exhibiting reduced
variation in oxidation-reduction potential before and after storage at a relatively
high temperature and reduced variation in gamma balance, leading to superior storage
stability. Generally, a variation in gamma balance of more than 10% results in
a change in print density, producing problems in practical use.
It was further proved that a molar ratio of Na:k was required for at least 3:1,
more preferably at least 4:1, and still more preferably Na salt was 100%.
It was also proved that the molar ratio of SO4:CO3 was preferably required to
be least 0.25, and more preferably in the range from a low of 0.30 to a high of 1.0.
Example 2
Experiments were carried out similarly to Example 1, except that EDTA.4H
added to the concentrated color developer composition in experiment No. 5 in Example
1 was changed to the compounds to be equimolar as shown in Table 2. Results thereof
are shown in Table 2.
| |
|
|
|
Gamma |
|
| |
|
|
ΔE |
balance |
| |
|
|
variation |
change |
| |
No. |
Additive |
(%) |
rate (%) |
Remarks |
| |
| |
2-1 |
None |
8.9 |
9.4 |
Inv. |
| |
2-2 |
HEDP |
9.0 |
9.2 |
Inv. |
| |
2-3 |
Hexameta- |
8.8 |
9.4 |
Inv. |
| |
|
phosphoric acid |
| |
2-4 |
Citric acid |
9.3 |
9.7 |
Inv. |
| |
2-5 |
A-I-1 |
6.2 |
6.9 |
Inv. |
| |
2-6 |
A-I-3 |
6.5 |
7.2 |
Inv. |
| |
2-7 |
A-I-14 |
6.8 |
7.5 |
Inv. |
| |
2-8 |
A-II-1 |
7.1 |
7.8 |
Inv. |
| |
2-9 |
A-II-2 |
7.3 |
7.7 |
Inv. |
| |
2-10 |
A-III-1 |
7.4 |
7.5 |
Inv. |
| |
2-11 |
A-III-2 |
7.8 |
7.3 |
Inv. |
| |
2-12 |
A-III-13 |
7.9 |
7.9 |
Inv. |
| |
2-13 |
DTPA |
6.0 |
6.2 |
Inv. |
| |
2-14 |
TTHA |
6.3 |
6.5 |
Inv. |
| |
| |
Inv.: Present invention |
| |
HEDP = hydroxyethylidene disulfonic acid |
| |
DTPA = diethylenetriamine pentaacetic acid |
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