Radiation imagery chemistry: process – composition – or product th – Including control feature responsive to a test or measurement
Reexamination Certificate
2001-01-29
2002-11-12
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Including control feature responsive to a test or measurement
C430S265000, C430S398000, C430S399000, C430S440000, C430S441000, C430S442000, C430S435000, C430S485000, C430S578000, C430S592000
Reexamination Certificate
active
06479199
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for processing silver halide photographic light sensitive materials and in particular to a method for processing a silver halide photographic light sensitive material exhibiting higher sensitivity in the red to near infrared region for use in an image setter or facsimile plotter, resulting in little residual color stain when processed in a developer containing an ascorbic acid type developing agent, and exhibiting superior process stability.
BACKGROUND OF THE INVENTION
Photographic materials having photographic characteristics such as ultra-high contrast are broadly employed as a photographic material used in the field of printing plate making. To obtain such high contrast images, there are known an image forming method of processing photographic materials containing hydrazine derivatives with a so-called MQ developer solution (i.e., developer solution by the combined use of hydroquinone and p-amiophenols) or a PQ developer solution (i.e., developer solution by the combined use of hydroquinone and 1-phenyl-3-pyrazolodones) to form an ultra-high contrast image, as described in U.S. Pat. No. 4,269,929 and JP-A Nos. 60-258537 and 5-232616 (hereinafter, the term, JP-A refers to a unexamined, published Japanese Patent Application). In such an image forming method, however, hydroquinone is used as a developing agent, and it is a concern that hydroquinone is not suitable from the ecological or toxicological point of view. It is therefore an aim to achieve a method of forming ultra-high contrast images with a developer solution containing no hydroquinone.
U.S. Pat. Nos. 5,236,816 and 5,264,323 describe a system in which ascorbic acids are employed as a developing agent. However, problems arise with the use of ascorbic acids as a developing agent in that the pH of a developer is easily lowered through processing and aerial oxidation and process variation is quite marked. There is a problem that the use of ascorbic acid developing agents increases residual color-staining caused by sensitizing dyes, and consequently an improvement thereof is desired. Further, the use of ascorbic acid developing agents produces silver precipitates in the fixer bath, which adheres to photographic materials as silver sludge, and reduction of such sludge is also desired.
SUMMARY OF THE INVENTION
In view of the foregoing problems, it is an object of the present invention to provide a method for processing a silver halide photographic light sensitive material for use in graphic arts, achieving a decrease in residual dye staining after processing, leading to enhanced sensitivity and contrast, and also superior halftone dot quality and practical density within the red to infrared wavelength region, and producing little sludge.
The object of the present invention can be accomplished by the following constitution:
1. a method of processing a silver halide photographic light sensitive material comprising the steps of:
developing the silver halide photographic material with a developer solution,
fixing the developed silver halide photographic material with a fixer solution, and
washing the fixed silver halide photographic material with a washing water,
wherein the silver halide photographic material comprises a support and a light sensitive silver halide emulsion layer containing a spectral-sensitizing dye represented by the following formula (1-a), (1-b), (2), (3-a), (3-b), (4) or (5),
and wherein the developer solution contains a developing agent represented by formula (A), and at least one of the developer and fixer solutions is replenished at a replenishing rate which has been determined in accordance with the proportion of an exposed area per unit area of the photographic material:
wherein Y
21
, Y
22
, Y
23
and Y
24
each represent —N(R
24
)—, —O—, —S—, —Se— or —Te—, provided that one of Y
23
and Y
24
is —N(R
24
)—, and all of Y
21
, Y
22
and Y
23
or all of Y
21
, Y
22
and Y
24
are not —S—; R
21
represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R
22
, R
23
and R
24
each represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R
22
, R
23
and R
24
are substituted with an aqueous solubility promoting group; Z
21
represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W
21
represents an oxygen atom, sulfur atom, =N(Ar) or =C<(E
21
) (E
22
), in which Ar represents an aromatic ring group or a heterocyclic group, E
21
and E
22
represent an electron-withdrawing group or combine with each other to form a heterocyclic ring containing an oxo group or an acidic heterocyclic ring; L
21
and L
22
represent a substituted or unsubstituted methine group; 121 is 0 or 1; M
21
represent an ion necessary to counterbalance a total intramolecular charge; and n21 represents a number of ion necessary to counterbalance a total intramolecular charge;
wherein Y
25
, Y
26
and Y
27
each represent —N(R
29
)—, —O—, —S—, or —Se—; R
25
represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R
26
, R
27
, R
28
and R
29
represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least three of R
26
, R
27
, R
28
and R
29
are substituted with an aqueous solubility promoting group; Z
22
represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; L
23
and L
24
represent a substituted or unsubstituted methine group; M
22
represent an ion necessary to counterbalance a total intramolecular charge; and n22 represents a number of ion necessary to counterbalance a total intramolecular charge;
wherein Y
31
, Y
32
and Y
33
each represent —N(R
34
)—, —O—, —S—, or —Se—; R
31
represents an aliphatic group having 10 or less carbon atoms and substituted with an aqueous solubility promoting group; R
32
, R
33
and R
34
represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R
32
, R
33
and R
34
are substituted an aqueous solubility promoting group; V
31
and V
32
each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, or V
31
and V
32
combine with each other to form a ring condensed with an azole ring; L
31
and L
32
represent a substituted or unsubstituted methine group; M
31
represent an ion necessary to compensate a total intramolecular charge; and n31 represents a number of ion necessary to counterbalance a total intramolecular charge;
wherein Y
41
and Y
42
each represent —N(R
44
)—, —O—, —S—, —Se— or —Te—; R
41
represents an aliphatic group having 8 or less carbon atoms and substituted with an aqueous solubility promoting group; R
42
, R
43
and R
44
represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R
42
, R
43
and R
44
are substituted with an aqueous solubility promoting group; Z
41
represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W
41
represents an oxygen atom, sulfur atom, =N(Ar) or =C<(E
21
)(E
22
), in which Ar represents an aromatic ring group or a heterocyclic group, E
41
and E
42
represent an electron-withdrawing group or E
41
and E
42
combine with each other to form a heterocyclic; L
41
, L
42
, L
43
and L
44
represent a substituted or unsubstituted methine group; 141 is 0 or 1; M
41
represent an ion necessary to counterbalance a tot
Bierman, Muserlian and Lucas
Konica Corporation
Schilling Richard L.
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