Radiation imagery chemistry: process – composition – or product th – Nonradiation sensitive image processing compositions or... – Developer
Reexamination Certificate
2002-03-14
2004-01-27
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Nonradiation sensitive image processing compositions or...
Developer
Reexamination Certificate
active
06682881
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to an antifoaming agent composition for silver halide photographic (black-and-white and color) processing solution and more particularly to an antifoaming agent composition that can be preferably used for first black-and-white developer for silver halide reversal color photograph and/or its replenisher. Even more particularly, the present invention relates to an antifoaming agent composition for use in the minimization of developer streaks caused by foam produced in the developer and a process for the processing of a silver halide photographic material using the composition.
BACKGROUND OF THE INVENTION
A silver halide color reversal photographic material which has been exposed is then normally subjected to 1st black-and-white development, fogging, reversal color development and desilvering to form a reversal color image thereon. The silver halide photographic material comprises various surface active agents incorporated therein so that these surface active agents are eluted with the developer during development to make it easy for the developer to be bubbled. The developer is agitated by nitrogen or air ejected from the bottom of the bath to develop uniformly the photographic material However, this causes the accumulation of bubbles on the surface of the developer. Accordingly, when the photographic light-sensitive material enters into the development bath, these bubbles are attached to the photographic light-sensitive material, causing bubble-like developer streaks. This bubble-like developer streaks can easily occur particularly in the 1st black-and-white development of silver halide color reversal photographic material. Thus, this problem has awaited solution. Further, bubbles produced in the developer can be easily attached particularly to the photographic light-sensitive material in a process involving the successive development of individual photographic light-sensitive materials fixed in vertical position (hereinafter referred to as “hanging development”).
Examples of the antifoaming agent to be incorporated in the developer include those produced by Fuji Photo Film Co., Ltd., and KODAK Defoamer Process E-6 (produced by Eastman Kodak Company). All these antifoaming agents contain a siloxane- or silicon-based compound, which can very hardly be dissolved in water, causing the production of suspended matters on the surface of the developer or stain inside the bath. Thus, an antifoaming agent having a higher water solubility than these compounds which still exerts the desired antifoaming effect has been desired. Further, the existing antifoaming agents are added to the developer as they are, but the antifoaming components are suspended on the surface of the bath or attached to the inner wall of the replenisher bath when added to the developer replenisher, making it impossible for the antifoaming components to be supplied into the developer in the development bath. Thus, no antifoaming effect can be exerted.
On the other hand, Japanese Patent Laid-Open No. 1993-88326 discloses a method which comprises processing a photographic light-sensitive material with a color developer containing at least one specific fluorine-based compound but substantially free of sulfite ion so that the variation of photographic properties during continuous processing and the production and growth of deposits in the processing bath can be inhibited. As described in the above cited patent, the developer substantially free of sulfite ion (The term “substantially free of sulfite ion” indicates that sulfite ion is incorporated in an amount of not greater than 3 mmol/l as described in line 3-line 4, left column, page 9 of the above cited patent) gives less variation of photographic properties and causes remarkably lessened production of deposits in the processing bath if it comprises the fluorine-based compound described in the above cited patent incorporated therein. However, a developer containing sulfite ion (normally in an amount of from 100 to 200 mmol/l) such as 1st black-and-white developer for silver halide reversal color photograph can provide no such an effect even if it comprises the fluorine-based compound described in the above cited patent incorporated therein.
Further, Japanese Patent Laid-Open No. 1996-201994 discloses a developer containing at least one amino acid derivative-based surface active agent and a developer containing at least one amino acid derivative-based surface active agent and at least one fluorine-based surface active agent. This approach allows the reduction of occurrence of developer streaks caused when the surface of a silver halide photographic material is stained by fingerprint or the like. However, the foregoing amino acid derivative-based surface active agent cannot be incorporated in the 1st black-and-white developer for reversal color photograph because it causes the variation of photographic properties. Further, as described in the above cited patent (line 20-line, right column, page 2), this approach is disadvantageous in that the addition of a fluorine-based surface active agent to the developer causes turbidity/precipitation that causes the attachment of stain to the surface of the photographic light-sensitive material, accelerating uneven processing.
Under these circumstances, an antifoaming agent having an excellent antifoaming effect and stability which can be used in the processing of reversal color photograph as well has been desired.
The inventors earlier found that a fluorine-based surface active agent containing a perfluoroalkyl group having a specific structure exerts a great antifoaming effect and causes neither turbidity/precipitation nor processing stain even when incorporated in the 1st black-and-white developer for reversal color photograph. The inventors then proposed this fluorine-based surface active agent as an antifoaming agent composition for silver halide photographic processing, particularly for reversal color photographic processing, which can meet the foregoing demand of the market in Japanese Patent Laid-Open No. 2000-112095. This fluorine-based surface active agent containing such a perfluoroalkyl group exerts a desirable effect on the solution to the foregoing problems such as antifoaming capacity for color photographic processing and inhibition of turbidity or precipitation.
On the other hand, the color reversal photographic light-sensitive material tends to be slowly developed at highly-exposed area at the 1st development step. Thus, the resulting highlighted area tends to become less hard. Accordingly, when development is accelerated, less exposed area is overdeveloped, making it difficult to balance the progress of development. The solution to this problem has been a long time assignment in the technique for emulsion of photographic light-sensitive material and the technique of 1st development. Some surface active agents have a good or adverse effect on the progress of development. The foregoing fluorine-based surface active agent containing a perfluoroalkyl group has no effect or an effect of inhibiting the process of development. If a surface active agent which can be used as an antifoaming agent has a desirable effect on the progress of development to improve the gradation of highlighted area, its value is extremely great.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a technique which can exert the foregoing effect of improving gradation while maintaining the effect of eliminating foam in the developer and the stability high enough to prevent deposition embodied in the above cited Japanese Patent Laid-Open No. 2000-112095. In some detail, an object of the present invention is to provide a composition and antifoaming process which can raise the gradation of highlighted area, eliminate the occurrence of turbidity or precipitation in the developer and lessen developer streaks caused by bubbles produced in the developer, particularly 1st reversal color photographic black-and-white developer.
Another object of the present invention is to
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