Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2000-09-18
2002-10-01
Baxter, Janet (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S544000, C430S546000, C430S599000, C430S600000, C430S601000, C430S607000, C430S551000
Reexamination Certificate
active
06458522
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material and an image forming method using the light-sensitive material. Particularly, the present invention relates to a silver halide light-sensitive material that is used in the fields of graphic art, and to an image forming method to form a ultra-high contrast photographic image using the light-sensitive material.
BACKGROUND OF THE INVENTION
The photomechanical process in the field of graphic arts includes a process of converting a photographic original image in continuous gradation to a dot image. In order to improve reproduction of the image, a technique of forming an ultra-high contrast image has been used.
Image formation systems capable of obtaining ultra-high contrast photographic properties through development with a processing solution having good storage stability are disclosed, for example, in U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,272,606, and 4,311,781. These methods are a system of forming an ultra-high contrast image by processing a silver halide light-sensitive material, having incorporated therein a specific acylhydrazine compound, with a developing solution containing 0.15 mole/liter or more of a sulfuric acid salt preservative and having a pH ranging from 11.0 to 12.3.
In order to complete a high-contrast image formation using hydrazine derivatives, it is necessary to process with a developing solution having a pH of 11 or more, usually 11.5 or more.
However, developing solutions having a high pH value of pH 11 or more, even though they contain preservatives, are prone to air oxidation and are unstable. Therefore, such a developing solution needs a large amount of replenishment in order to maintain good photographic properties in running use over a long period of time. An image formation system capable of obtaining an ultra-high contrast image, even in a processing with a developing solution having a pH of less than 11, in order to compensate for such a defect, is disclosed as described below. For example, the development of hydrazine derivatives capable of minimizing the variation width of photographic properties ascribable to the change in the pH of the developing solution, the use of a nucleation development accelerator for acceleration of hard gradation enhancement, or the like is attempted, to achieve such an image formation system.
For example, JP-A-62-222241 (the term “JP-A-” as used herein means an unexamined published Japanese patent application), JP-A-62-250439, JP-A-62-280733, and the like disclose nucleation accelerators for acceleration of hard gradation enhancement. A high-contrast image showing a certain level of photographic properties can indeed be attained by incorporating these nucleation accelerators, in combination with a specific hydrazine derivative, in a light-sensitive material. However, light-sensitive materials prepared by such a previous method are not fully satisfactory, in view of deterioration of dot image quality, because they cause a sand-like or spot-like fogging, so-called “black spots,” which are made of fine developed silver, at the non-image portion that is not exposed.
The black spots are apt to occur when, particularly by aerial oxidation of a developing solution, a rise in pH of the solution, and/or a reduction in the concentration of sulfuric acid therein, is caused.
JP-A-1-179939 and JP-A-1-179940 describe a method of processing a light-sensitive material containing a nucleation development accelerator having a group adsorptive onto silver halide emulsion particles and a nucleating agent having the same adsorptive group, with a developing solution having a pH of 11 or less. U.S. Pat. No. 4,975,354 discloses that an effect on acceleration of hard gradation enhancement can be attained by processing a light-sensitive material containing a secondary or tertiary amine compound having a repeating unit of ethylene oxide in combination with a hydrazine compound, with a developing solution having a pH of 11.4.
JP-A-6-242534 discloses a method of forming a high-contrast image that shows a gamma value of 10 or more, by processing a light-sensitive material containing a bis-type heterocyclic N-quaternary onium salt and a hydrazine compound, with a developing solution having a pH of 11 or less.
Further, JP-A-10-90841 describes bispyridinium salt development accelerators in which pyridinium moieties are connected via an alkylene group. However, it is also difficult to obtain satisfactory high-contrast photographic properties by using these compounds with a developing solution having a low pH in particular. Further, JP-A-10-90841 and JP-A-10-39444 disclose bispyridinium salt and bis-isoquinolinium salts, each of which has a recurring unit of 4 to 18 ethyleneoxy groups. However, the compounds disclosed therein fail to reach a satisfactory level, even though somewhat high-contrast photographic properties can be attained thereby.
SUMMARY OF THE INVENTION
Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material that has improved photographic properties. A secondary object of the present invention is to provide a silver halide photographic light-sensitive material that is capable of obtaining photographic properties of high-contrast negative gradation having a gamma (&ggr;) value exceeding 10, by the use of a stable developing solution, and further that is excellent in image quality. A third object of the present invention is to provide a silver halide photographic light-sensitive material that is excellent in reproducibility of an original. A fourth object of the present invention is to provide a silver halide photographic light-sensitive material showing, in addition to the foregoing, less variation in sensitivity, &ggr; value, and Dmax, without increasing black spots, even though the light-sensitive material is processed with a developing solution in which the concentration of sulfurous acid preservative has been reduced, or in which the pH value has been changed, due to fatigue over time, or a developing solution in which the pH value has been changed and/or the bromide ion concentration has been increased by processing a large amount of films. Further, a fifth object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material, which method is capable of obtaining a negative image having an ultrahigh contrast and improved photographic properties, by use of a developing solution having a lower pH than the previous pH which has been used in the past.
Other and further objects, features, and advantages of the invention will appear more fully from the following description.
DETAILED DESCRIPTION OF THE INVENTION
The foregoing objects of the present invention have been achieved with the following constructions of (1) to (7).
(1) A silver halide photographic light-sensitive material comprising at least a light-sensitive silver halide emulsion layer applied on a support, wherein said emulsion layer or another hydrophilic colloidal layer comprises at least one kind of compounds selected from a group consisting of a quaternary nitrogen or phosphorus salt compound, having 20 or more of total recurring units consisting of an ethyleneoxy group and/or a propyleneoxy group in a molecule; a quaternary salt compound represented by the following formula (A); and a quaternary salt compound represented by the following formula (B):
wherein Q represents a nitrogen atom or a phosphorus atom, R
1
, R
2
and R
3
each independently represent an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a heterocyclic group, L
1
represents an alkylene group, Y represents —C(═O) or —SO
2
—, L
2
represents a divalent connecting group having at least one hydrophilic group, X
n−
represents an n-valent counter anion, and n represents an integer of 1 to 3, provided that X
n−
can be omitted when another anionic group exists in a molecule and forms an intramolecular salt with P
&pl
Kuwabara Ken-ichi
Taniguchi Masahiko
Yamada Kohzaburoh
Yamaguchi Tetsuo
Fuji Photo Film Co. , Ltd.
Sughrue & Mion, PLLC
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