Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2000-03-23
2001-11-06
Chea, Thorl (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S585000
Reexamination Certificate
active
06312884
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the field of photographic elements, and in particular to photographic elements with reduced sensitizing dye stain.
BACKGROUND OF THE INVENTION
In photographic systems, sensitizing dyes that are not removed during processing may give rise to undesirable background stain. Additionally, many sensitizing dyes are used in their J-aggregate state. Such aggregation tends to increase the difficulty in removal of the dyes during processing.
SUMMARY OF THE INVENTION
We have discovered a class of dyes which gives rise to unexpectedly low levels of post-process dye stain. This low staining property is maintained, even when dyes of this type are used in their J-aggregate state. For instance, in a color negative application, there is a need for efficient J-aggregating sensitizing dyes for the short red spectral region (590-640 nm) which give rise to minimal post-process dye stain. These requirements can be met by dyes of the present invention.
One aspect of the invention comprises a photographic element comprising a light sensitive silver halide emulsion layer which contains a sensitizing dye of the formula:
wherein:
n is 0 or 1;
X, Y, and Z are independently O, N, S, Se, or C;
X′ is O, NR
13
, S, or Se;
R
1
and R
2
are acid substituted alkyl;
R
4
is H or alkyl, with the proviso that if X′ is N R
13
, R
4
is H;
each of R
6
, R
7
, R
8
and R
9
is independently H or a substituent or R
7
and R
8
or R
8
and R
9
together with the carbon atoms to which they are attached form a 5-membered or 6-membered ring;
when X or Y or Z is O, N, S or Se then a, b or c, respectively, is 0 and when X or Y or Z is C, a, b or c, respectively is 1 and the corresponding R
10
, R
11
, or R
12
substituent is independently H or a non-aromatic substituent; and
R
13
is alkyl or substituted alkyl.
DETAILED DESCRIPTION OF THE INVENTION
As set forth above this invention provides photographic elements with reduced dye stain. The dyes are of the general formula:
wherein:
n is 0 or 1;
X, Y, and Z are independently O, N, S, Se, or C;
X′ is O, NR
13
, S, or Se;
R
1
and R
2
are acid substituted alkyl; acid salt groups include carboxy, sulfo, phosphato, phosphono, sulfonamido, sulfamoyl, or acylsulfonamido (groups such as —CH
2
—CO—NH—SO
2
—CH
3
) groups. Note that reference to acid or acid salt groups are used to define only the free acid groups or their corresponding salts, and do not include esters where there is no ionizable or ionized proton. Particularly preferred are the carboxy and sulfo groups (for example, 3-sulfobutyl, 4-sulfobutyl, 3-sulfopropyl, 2-sulfoethyl, carboxymethyl, carboxyethyl, carboxypropyl and the like);
R
4
is H or alkyl, with the proviso that if X′ is N R
13
, R
4
is H;
each of R
6,
R
7
, R
8
and R
9
is independently H or a substituent or R
7
and R
8
or R
8
and R
9
together with the carbon atoms to which they are attached form a 5-membered or 6-membered ring; “Examples of substituents are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a halogen atom, an acylamino group, a carbamoyl group, a carboxy group, or an alkoxy group;”
when X or Y or Z is O, N, S or Se then a, b or c, respectively, is 0 and when X or Y or Z is C, a, b or c, respectively, is 1 and the corresponding R
10
, R
11
, or R
12
substituent is independently H or a non-aromatic substituent; and
R
13
is alkyl or substituted alkyl.
Non-aromatic substituents include, for example, alkyl, alkenyl, cycloalkyl, non-aromatic carbocyclic substituents, such as cycloalkyl, non-aromatic heterocyclic substituent, such as cyclic ethers, and the like. Each of these substituents may be further substituted with, for example, halogens, alkoxy groups, alkoxycarbonyl groups, etc.
In preferred embodiments of the invention, Y is N or C, Z is C and X is S.
Particularly preferred are dyes of the formula:
where R
1
, R
2
, R
4
, R
6,
R
7
, R
8
, R
9
, R
10
, R
11
, a, b and X′ have the same meaning as above and Y is N or C.
Non-limiting examples of preferred dyes are shown below.
The sensitizing dyes used in the invention can be synthesized by one skilled in the art by known methods, for example procedures described in F. M. Hamer,
Cyanine Dyes and Related Compounds,
1964 (publisher John Wiley & Sons, New York, N.Y.) and
The Theory of the Photographic Process,
4
th
edition, T. H. James, editor, Macmillan Publishing Co., New York, 1977. Synthetic examples are given below.
The emulsion layer of the photographic element of the invention can comprise any one or more of the light sensitive layers of the photographic element. The photographic elements made in accordance with the present invention can be black and white elements, single color elements or multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
Photographic elements of the present invention may also usefully include a magnetic recording material as described in
Research Disclosure,
Item 34390, November 1992, or a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support as in U.S. Pat. Nos. 4,279,945 and U.S. Pat. No. 4,302,523. The element typically will have a total thickness (excluding the support) of from 5 to 30 microns. While the order of the color sensitive layers can be varied, they will normally be red-sensitive, green-sensitive and blue-sensitive, in that order on a transparent support, (that is, blue sensitive furthest from the support) and the reverse order on a reflective support being typical.
The present invention also contemplates the use of photographic elements of the present invention in what are often referred to as single use cameras (or “film with lens” units). These cameras are sold with film preloaded in them and the entire camera is returned to a processor with the exposed film remaining inside the camera. Such cameras may have glass or plastic lenses through which the photographic element is exposed.
In the following discussion of suitable materials for use in elements of this invention, reference will be made to
Research Disclosure,
September 1996, Number 389, Item 38957, which will be identified hereafter by the term “Research Disclosure I.” The Sections hereafter referred to are Sections of the Research Disclosure I unless otherwise indicated. All Research Disclosures referenced are published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND. The foregoing references and all other references cited in this application, are incorporated herein by reference.
The silver halide emulsions employed in the photographic elements of the present invention may be negative-working, such as surface-sensitive emulsions or unfogged internal latent image forming emulsions, or positive working emulsions of the internal latent image forming type (that are fogged during processing). Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V. Color materials and development modifiers are described in Sections V through XX. Vehicles which can be used in the photographic elements are described in Section II, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections VI through XIII. Manufacturing methods are described in all of the sections, layer arrangements particularly in Section XI, exposure altern
Link Steven G.
Mee John D.
Chea Thorl
Eastman Kodak Company
Rice Edith A.
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