PatentDe  


Dokumentenidentifikation EP0599381 24.02.2000
EP-Veröffentlichungsnummer 0599381
Titel Farbstoffverbindungen und photographische Silberhalogenidelemente, die diese enthalten
Anmelder Eastman Kodak Co., Rochester, N.Y., US
Erfinder Parton, Richard Lee, Rochester, US;
Stegman, David Alan, Rochester, US;
Sauter, Frederick Joseph, Rochester, US
Vertreter derzeit kein Vertreter bestellt
DE-Aktenzeichen 69327634
Vertragsstaaten DE, FR, GB
Sprache des Dokument EN
EP-Anmeldetag 16.11.1993
EP-Aktenzeichen 932031909
EP-Offenlegungsdatum 01.06.1994
EP date of grant 19.01.2000
Veröffentlichungstag im Patentblatt 24.02.2000
IPC-Hauptklasse G03C 1/12
IPC-Nebenklasse G03C 1/18   G03C 1/16   G03C 1/20   C09B 23/02   

Beschreibung[en]
Field of the Invention

This invention relates to dyes and silver photographic elements containing such dyes as sensitizing dyes.

Background of the Invention

Silver halide photography usually involves the exposure of silver halide photographic element with light in order to form a latent image that is developed during photographic processing to form a visible image. Silver halide is intrinsically sensitive only to light in the blue region of the spectrum. In order to sensitize the silver halide to other than the blue region, sensitizing dyes are used in the silver halide emulsion. Sensitizing dyes are chromophoric compounds (usually cyanine dye compounds). Their usual function is to adsorb to the silver halide and to absorb light (usually other than blue light) and transfer that energy via an electron to the silver halide grain thus, rendering the silver halide sensitive to radiation of a wavelength other than the blue intrinsic sensitivity. However, sensitizing dyes can also be used to augment the sensitivity of silver halide in the blue region of the spectrum.

Generally a sensitizing dye should wash out of the film or paper during processing. Any retained dye contributes to Dmin and this is often referred to as sensitizing dye stain. Dye stain, which adversely affects the image recorded in the photographic material, has been a source of concern for many years. The problem of retained sensitizing dye stain has been aggravated by the advent of new emulsions, such as tabular grains, which have more surface area and use higher dye levels and accordingly tend to give higher levels of dye stain. Additionally, the use of high chloride emulsions makes preferable the use of sensitizing dyes having enhanced adsorption to silver halide since sensitizing dyes tend to be inherently less well adsorbed to silver chloride emulsions. This can also lead to higher levels of dye stain. Such high chloride emulsions are also often subjected to rapid processing, which can further aggravate dye stain problems.

In order to reduce dye stain, stain-reducing agents, such as bis-triazine stilbene compounds, also known as optical brighteners, have been used to reduce dye stain. These compounds, however, are expensive and can be difficult to incorporate in the hydrophilic layers of photographic materials. Another method for reducing dye stain in some cases, is to incorporate certain substituents into the dye molecule to reduce dye stain. For example, dyes containing N,N'-2-hydroxy-3-sulfopropyl nitrogen substituents (J. Gotze, et al., U.S. patent number 3,424,586) are generally less retained than the corresponding dyes with 3-sulfopropyl groups. Other stain-reducing nitrogen substituents have also been disclosed such as the 2-sulfoethylcarbamoylmethyl groups disclosed in U.S. patent number 5,091,298 to Parton et al. EP-A-0451816 discloses photographic elements having high sensitivity and low dye stain comprising a carbocyanine dye, which does not contain both an amide group and an aromatic ring.

Although the foregoing dye structure modifications can be effective at reducing dye stain they have not eliminated the problem. New substituents are always desirable which will result in dyes with low dye stain. In addition, there is an important class of green sensitizers for which it is not possible to use these types of stain-reducing nitrogen substituents. In particular, benzoxazole dyes (an example is given in Formula A below) are commonly used to afford green sensitization in many photographic products such as color negative and reversal films, and color paper.

In many instances, benzoxazole dyes also produce undesirable post-process stain. However, it has not been possible to incorporate the aforementioned stain-reducing nitrogen substituents on these dyes because the benzoxazole nucleus is too reactive. For instance, attempts to place a 2-hydroxy-3-sulfopropyl substituent, a 2-sulfoethylcarbamoylmethyl or similar group on the benzoxazole nucleus result in ring-opening of the benzoxazole. Thus, alternative stain reducing substituents are especially needed for dyes containing the benzoxazole nucleus.

It is thus an object of this invention to provide new dye compounds useful as sensitizing dyes for silver halide photographic elements, which dyes have relatively low dye stain. It is a further object of this invention to provide new benzoxazole sensitizers which exhibit relatively low dye stain.

Summary of Invention

The present invention provides cyanine dyes of the structure:

wherein:
  • X1 and X2 each independently represent the atoms necessary to complete a benzo-condensed 5- or 6-membered heterocyclic nucleus, which, in addition to being substituted by Z1 and Z2 respectively, may be further substituted or unsubstituted;
  • n is a positive integer from 1 to 4,
  • p and q each independently represents 0 or 1, each L independently represents a substituted or unsubstituted methine group,
  • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl,
  • Z1 represents a substituent which contains both an amide group and an aromatic ring which may be appended or fused to X1 but does not contain a heterocyclic 5-membered ring which has more than one heteroatom a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, and t2 represents H or a substituent; and
  • W1 is a counterion as needed to balance the charge of the molecule.

Photographic elements of the above described structure with the defined Z1 substituents, produce good sensitizing and low dye stain, particularly in a color format, than corresponding dyes not having a substituent of the Z1 type.

The present invention further provides silver halide photographic elements comprising a sensitizing dye of formula I.

Detailed Description of Embodiments of the Invention

In dyes of the type of formula I, it will be understood that the term "amide" when used without reference to substituent locations on such a group, broadly refers to a group containing the atoms -CON- and includes carbamoyl groups, although either term when used with reference to substituents may be limited to specific structural arrangements. For example, Z1 is preferably is an arylamide or arylcarbamoyl. This means that Z1 preferably has either of the respective structures (each of which is broadly an "amide"):

wherein the Ar (an aromatic ring) may be further bonded. The definition of aromatic rings is described in J. March, Advanced Organic Chemistry, Chapter 2, (1985 , John Wiley & Sons). The aromatic ring can be a hydrocarbon or heterocyclic. In addition, by reference to "heteroatom" in the definition of Z1 above, is meant an atom other than carbon.

Examples of Z1 include those where the aromatic ring is phenyl, furan-2-yl, furan-3-yl, 1-H-pyrrol-2-yl, 1-H-pyrrol-3-yl, thiophen-2-yl or thiophen-3-yl. Furthermore, the aromatic ring of Z1 or Z2 may be appended or fused to X1 or X2, or may be indirectly bonded thereto for example, through a substituted or unsubstituted group although any linking group should preferably maintain the relatively planar shape of the Z1-X1 group. For example, the linking group is an alkylene group. Further, any chain linking the aromatic ring of Z1 or Z2 to X1 or X2 is preferably no more than 4, 3 or 2 atoms in length (including the N and C of an amide group).

Optionally, Z1 does not contain a hydroxyarylacyl group of formula HO-Ar-CO- in which Ar is an aromatic ring, where Ar may optionally be appended or fused to X1 (particularly an α-hydroxyarylacyl group of this formula).

The photographic element which contains dyes of the present invention may particularly be those of a type which preferably have a water-immiscible dispersion into which the sensitizing dye can at least partially migrate. For example, the photographic element may be a color photographic element having a layer (usually, but not necessarily the same layer which contains silver halide and the sensitizing dye) which contains a color coupler dispersion into which the dye could at least partially migrate.

Preferably the sensitizing dyes have the formula:

  • X1 and X2 independently represent the atoms necessary to complete a benzothiazole nucleus, benzoxazole nucleus, benzoselenazole nucleus, benzotellurazole nucleus, quinoline nucleus or benzimidazole nucleus, which, in addition to being substituted by Z1 and Z2 respectively, may be further substituted or unsubstituted,
  • n is a positive integer from 1 to 4, each L independently represents a substituted or unsubstituted methine group,
  • Z1 represents a substituent which contains both an amide group and an aromatic ring, and Z2 represents H or a non-aromatic substituent;
  • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl;
  • W1 is a counterion as needed to balance the charge of the molecule.

Other prefered dyes of this invention are of formula II:

in which Q1 and Q2 are, independently, O, N, S or Se. Dyes of structure II are particularly useful when at least one nucleus is a benzoxazole (that is, at least Q1 or Q2 is O) or, more preferably, when both nuclei are benzoxazoles. Z1 is preferably a 5-position substituent, that is Z1 is positioned as shown:
Z1 preferably has one of the following structures:
  • Y1-CONR3-*; Y1-NR4-CO-*;
  • R5R6N-CO-Y2-* or R7-CO-NR8-Y2-*
wherein * represents the bonding position to X1; Y1 and Y2 are substituted or unsubstituted aromatic groups and R3, R4, R5, R6, R7 and R8 are independently substituted or unsubstituted lower alkyl. By "lower alkyl" is meant having 1 to 6 carbon atoms. Y1, for example, may be a substituted benzene, furan, pyrrole or thiophene ring and Y2 may be a substituted benzene ring.

The stricture of sensitizing dyes of the present invention are further preferably of the form:

In formula III R1, R2, Z1 and Z2 may be as already defined, although it is preferred that R1 and R2 represent lower alkyl each substituted with an acid or acid salt group. R9 may include H, alkyl, alkylene, alkoxy and the like, but is preferably a lower alkyl. In addition Z1 may be a substituent which contains both an aromatic and an amide group, and Z2 is H or another substituent which is preferably non-aromatic (for example, a halogen such as chlorine or fluorine). Z1 and Z2 are preferably on the 5-position of their respective rings, that is the formula would be:

Further, Z1 may more specifically be of the formula: Y1-CONH-* or Y1-NH-CO-* or G-Y2-* in which * indicates the point of attachment to the benzene ring of the nucleus, and Y1 may be as already defined or may more specifically be phenyl, furan-2-yl, 1-H-pyrrol-2-yl, 1-H-pyrrol-3-yl, thiophen-2-yl or thiophene-3-yl; and Y2 is 1,4-phenylene or 1,3-phenylene, G is acetamido. Additionally, Z2 may be a halogen. W3 is a counterion as needed to balance the charge of the molecule.

It is preferred that Z1 and Z2 not be a substituent which carries an antifoggant, particularly one of the type in US 5,032,500, or a hydrazide compound, particularly one of the type of US 4,800,154.

In any of the above formulae, X1 and X2 may independently be a nucleus which is a benzothiazole, benzoxazole, benzoselenazole, benzotellurazole, quinoline, benzimidazole , napthothiazole, napthiazole, or napthotellurazole. Any of those nuclei may be substituted with known substituents, such as halogen (e.g., chloro, fluoro, bromo), hydroxy, alkoxy (e.g. methoxy, ethoxy), substituted or unsubstituted alkyl (e.g. methyl, trifluoromethyl), alkenyl, thioalkyl (for example, methylthio or ethylthio), substituted and unsubstituted aryl (e.g. phenyl, 5-chlorophenyl) and others known in the art. Examples of substituents for the methine groups include alkyl (preferably of from 1 to 6 carbon atoms, e.g. methyl or ethyl) and aryl (e.g. phenyl). Additionally, substituents on the methine groups may form bridged linkages. The counterion, W1, which is present as necessary to balance the charge of the dye molecule may include known counterions such as sodium, potassium or triethylammonium.

R1 and R2 may independently represent substituted or unsubstituted aryl (preferably of 6 to 15 carbon atoms), or more preferably, substituted or unsubstituted alkyl (preferably of from 1 to 6 carbon atoms). Examples of aryl include phenyl and tolyl. Examples of alkyl include methyl, ethyl and propyl, as well as substituted alkyl groups (preferably a substituted lower alkyl containing from 1 to 6 carbon atoms) such as hydroxyalkyl group (for example, 2-hydroxyethyl; or a sulfoalkyl group such as 2-sulfobutyl and 3-sulfopropyl). The alkyl or aryl group may be substituted by one or more of the substituents on the above-described substituted alkyl groups. Examples of various Z1 include benzamido, 2-thiophenecarboxamido, 2-furancarboxamido 3-pyrrolecarboxamido, phenylcarbamoyl, 4-acetamidophenyl, 3-acetamidophenyl.

Examples of non-aromatic Z2 are halogen (e.g., chloro, fluoro, bromo), alkoxy,(e.g. methoxy, ethoxy), substituted or unsubstituted lower alkyl (e.g. methyl, trifluoromethyl) substituted or unsubstituted alkenyl. Alternatively, Z2 can independently be a substituted or unsubstituted aromatic ring that is fused with or appended to X2, such as phenyl or naptho, in which case, if n is equal to 1 or 2, R1 and R2 are also preferably 2-sulfoethyl groups. However, it is preferred that Z2 is a non-aromatic substituent since, as shown by the Examples below, such dyes generally tend to produce less dye stain.

Examples of compounds according to formula I include those listed in Table I:

Dye precursors can be made by techniques that are well-known in the art. For example, reaction of a 5-amino base with an aromatic (B) acid chloride affords an aromatic amide-substituted base.

Nitration of an aromatic (Ar) substituted base followed by reduction affords an amine. Reaction with an acid chloride affords an amide-substituted aromatic base.

Dyes of formula I can be prepared from the above dye precursers according to techniques that are well-known in the art, such as described in Hamer, Cyanine Dyes and Related Compounds, 1964 (publisher John Wiley & Sons, New York, NY) and James, The Theory of the Photographic Process 4th edition, 1977 (Easktman Kodak Company, Rochester, NY). The amount of sensitizing dye that is useful in the invention is preferably in the range of 0.1 to 4.0 millimoles per mole of silver halide and more preferably from 0.2 to 2.2 millimoles per mole of silver halide. Optimum dye concentrations can be determined by methods known in the art.

The silver halide used in the photographic elements of the present invention may be silver bromoiodide, silver bromide, silver chloride or silver chlorobromide. The silver halide used in the photographic elements of the present invention preferably contains at least 90% silver chloride or more (for example, at least 95%, 98%, 99% or 100% silver chloride). In particular, the possibility is also contemplated that the silver chloride could be treated with a bromide solution to increase its sensitivity, although the bulk concentration of bromide in the resulting emulsion will typically be no more than 2 to 2.5% and preferably between 0.6 to 1.2% (the remainder being silver chloride). The foregoing % figures are mole %.

The photographic elements of the present invention preferably use the sensitizing dye with tabular grain emulsions. Tabular silver halide grains are grains having two substantially parallel crystal faces that are larger than any other surface on the grain. Tabular grain emulsions are those in which greater than 50 percent of the total projected area of the emulsion grains are accounted for by tabular grains having a thickness of less than 0.3 µm (0.5 µm for blue sensitive emulsion) and an average tabularity (T) of greater than 25 (preferably greater than 100), where the term "tabularity" is employed in its art recognized usage as T = ECD/t2 where

  • ECD is the average equivalent circular diameter of the tabular grains in µm and
  • t is the average thickness in µm of the tabular grains.
The grain size of the silver halide may have any distribution known to be useful in photographic compositions, and may be ether polydipersed or monodispersed.

The silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure, (Kenneth Mason Publications Ltd, Emsworth, England) Item 308119, December, 1989 (hereinafter referred to as Research Disclosure I) and James, The Theory of the Photographic Process.

The photographic elements of the present invention, as is typical, provide the silver halide in the form of an emulsion. Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element. The emulsion can also include any of the addenda known to be useful in photographic emulsions.

The silver halide may be sensitized by dyes of the present invention by any method known in the art, such as described in Research Disclosure I. The dye may be added to an emulsion of the silver halide grains and a hydrophilic colloid at any time prior to (e.g., during or after chemical sensitization) or simultaneous with the coating of the emulsion on a photographic element. The dye/silver halide emulsion may be mixed with a dispersion of color image-forming coupler immediately before coating or in advance of coating (for example, 2 hours). Essentially any type of emulsion (e.g., negative-working emulsions such as surface-sensitive emulsions of unfogged internal latent image-forming emulsions, direct-positive emulsions such as surface fogged emulsions, or others described in, for example, Research Disclosure I) may be used. The above-described sensitizing dyes can be used alone, or may be used in combination with other sensitizing dyes, e.g. to also provide the silver halide with sensitivity to wavelengths of light outside the green region or to supersensitize the silver halide.

Other addenda in the emulsion and other photographic layers, may include those well-known in the art which are disclosed in Research Disclosure I and the references cited therein. The emulsion may also include brighteners, such as stilbene brighteners. Such brighteners are well-known in the art and are used to counteract dye stain, although the dyes of the present invention generally have low dye stain even if no brightener is used.

The emulsion layer containing silver halide sensitized with a dye of the present invention can be coated simultaneously or sequentially with other emulsion layers, subbing layers, filter dye layers, interlayers, or overcoat layers, all of which may contain various addenda known to be included in photographic elements.

Photographic elements of the present invention can be black and white but are preferably color. A color photographic element generally contains three silver emulsion layers or sets of layers (each set of layers often consisting of emulsions of the same spectral sensitivity but different speed): a blue-sensitive layer having a yellow dye-forming color coupler associated therewith; a green-sensitive layer having a magenta dye-forming color coupler associated therewith; and a red-sensitive layer having a cyan dye-forming color coupler associated therewith. Those dye forming couplers are provided in the emulsion typically by first dissolving or dispersing them in a water immiscible, high boiling point organic solvent, the resulting mixture then being dispersed in the emulsion. Suitable solvents include those in European Patent Application 87119271.2. Dye-forming couplers are well-known in the art and are disclosed, for example, in Research Disclosure I.

Photographic elements comprising the composition useful in the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known processing compositions, described, for example, in Research Disclosure I, or in James, The Theory of the Photographic Process 4th, 1977.

The invention is describe further in the following Examples.

Synthesis Example 1- Synthesis of Dye I-23 Intermediate A: 5-(2-Furancarboxamido)-2-methylbenzoxazole: 5-Amino-2-methylbenzoxazole (14.8 g, 0.100 mol) and 2,6-lutidine (12.0 g, 0.111 mol) were combined with 100 mL of tetrahydrofuran (THF) and the solution was cooled to 3 °C in an ice-bath under nitrogen. 2-Furoyl chloride (13.7 g, 0.105 mol) in 20 mL of THF was added dropwise so as to keep the temperature below 10 oC. After addition the ice-bath was removed and after stirring for 1 hour the mixture was poured into 300 mL of water. The solid was collected and washed with water and dried. This afforded 21.1 g (87% yield) of product; m.p. 156 - 158 oC.

Intermediate B: Anhydro-5-(2-furancarboxamido)-2-methyl-3-(4-sulfobutyl)benzoxazolium hydroxide:

5-(2-Furancarboxamido)-2-methylbenzoxazole (5.0 g, 0.021 mol) was combined with 1,4-butanesultone (3.0 mL, 0.029 mol) and 5 mL of butyronitrile and heated at reflux for 21 hours. The solid formed was collected and washed with acetone and dried (4.1 g, 52% yield).

Preparation of Anhydro-5-chloro-9-ethyl-5'-(2-furancarboxamido)-3'-(4-sulfobutyl)-3-(3-sulfopropyl)oxacarbocyanine hydroxide triethylammonium salt (Dye I-23):

Anhydro-5-(2-furancarboxamido)-2-methyl-3-(4-sulfobutyl)benzoxazolium hydroxide (2.5 g, 6.65 mmol) was combined with anhydro-5-chloro-2-(2-ethoxybutenyl)-3-(3-sulfopropyl)benzoxazolium hydroxide (2.5 g, 6.68 mmol) and 20 mL of m-cresol and heated to 127 oC. Triethylamine (5 mL) was added and the mixture was heated for 5 min. with stirring. The mixture was removed from the heat, chilled in an ice-bath, and diluted with ether. The orange oil that formed was dissolved in 50 mL of ethanol and potassium acetate (2.5 g) was added. The product precipitated and was collected. The dye was purified by treatment with hot methanol and then by dissolving it in m-cresol and methanol and re-precipitating it by adding acetone. This afforded 580 mg (12% yield) of dye; λ-max = 502 nm (MeOH), e-Max = 14.5 x 104.

Analysis Calculated for: C31H31ClO10N3S2K-1.5 H2O: C, 48.23; H, 4.41; N, 5.44.

Found: C, 48.21; H, 4.39; N, 5.37.

Photographic Evaluation Example 1:

Black and white photographic materials were prepared by coating a polyester support with a silver halide emulsion layer containing chemically-sensitized 0.2 µm cubic silver bromoiodide (2.6 mol % I) at 10.8 mg Ag/dm2, hardened gelatin at 73 mg/dm2, and sensitizing dye as identified in the Table III at 0.8 mmole/mole Ag. The elements were given a wedge spectral exposure and processed in RP X-OMAT (a trademark) chemistry (a developer containing hydroquinone and p-methylaminophenol as developing agents; this type of processing chemistry is described further in U.S. Patent No. 4,900,652).

The photographic speed of the dyes is reported in terms of a sensitizing ratio (SR), which is defined as the speed at λ-max (in log E units multiplied by 100) minus the intrinsic speed of the dyed emulsion at 400 nm (in log E units multiplied by 100) plus 200. This measurement of speed allows for comparison while using a uniform chemical sensitization that is not optimized for each sensitizing dye. The λ-max was determined from absorptance measurements.

Black and white stain was measured by placing the processed film in front of a scanning spectrophotometer. The total transmission was measured between 400 and 900 nm. This data was plotted as absorbance (-log 1/T). The stain was then calculated as the maximum absorbance at any wavelength in the range (Table IV).

Materials identified as "color" were prepared by coating a polyester support with a silver halide emulsion layer containing chemically-sensitized 0.7 µm (equivalent circular diameter) polymorphic silver bromoiodide (6 mole % I) at 16 mg Ag/dm2, hardened gelatin at 63 mg/dm2, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene antifoggant at 5 mg/dm2, a coupler (shown below) at 14 mg/dm2 in the coupler solvent di-m-butylphthalalate (8mg/dm2) and sensitizing dye as identified in Table IV at 0.4 mmole/mole Ag. The elements were given a wedge spectral exposure and coatings were processed in Kodak C-41® processing. The photographic speed of the dyes is reported in Table V as well as the sensitizing ratio (SR).

Color stain was obtained by processing unexposed color coatings for 3.5 minutes at 33 °C in the processing solution described below, followed by 1.5 minutes in a bleach-fix solution, and then a 3.5 minute wash. Stain was measured by placing the processed film in front of a scanning spectrophotometer. The stain was calculated as the maximum absorbance at any wavelength in the range 400 - 900 nm (Table V). In some cases, where more than one absorption peak was observed, the stain was calculated as the maximum absorbances at the wavelengths of the respective peaks. Processing Solution benzyl alcohol 14.2 mL potassium carbonate 28 g 45% potassium sulfite 2.75 mL triethanolamine 11 mL hydroxylamine sulfate 3.2 g potassium bromide 0.58 g potassium chloride 0.13 lithium chloride 0.13 anticalcium agent 0.8 Ml water to make 1.0 L pH adjusted to 10.08

All the dyes effectively sensitized the silver halide emulsions in which they were used. Comparison dyes are shown in Table II below. Stain figures are shown as Optical Density ("OD") x 103.

Dye Speed in the B&W Format Dye λmax SR Dye λmax SR C-1 547 250 I-3 537 238 I-1 542 249 I-4 540 240 I-2 541 243 I-9 542 229 I-6 530 229 I-10 530 231 I-7 538 236 I-14 527 222 I-8 546 242 I-18 542 241 I-13 541 238 I-26 543 241 I-16 541 247 I-27 535 231 I-20 541 237 I-33 537 242 I-21 546 249 C-4 547 244 I-23 547 248 I-5 539 236 I-24 545 245 I-11 492 232 I-31 548 247 I-15 543 247 I-32 546 249 I-19 539 244 I-37 541 263 I-22 495 231 I-38 544 254 I-29 545 244 C-2 538 235 Dye Speed in the B&W Format (Miscellaneous. Dyes). Dye λmax SR Dye λmax SR I-12 547 249 C-3 545 245 I-17 542 242 I-41 537 239 I-30 546 257 I-42 542 229 I-34 546 254 I-35 465 225 I-36 546 249
Dye Stain in the B&W Format Dye λmax ODx103 Dye λmax ODx103 C-1 508 48 I-4 505 42 I-1 510 41 I-9 508 46 543 31 I-2 510 41 I-10 508 50 550 61 I-6 510 47 I-14 505 44 I-7 508 51 I-18 508 39 I-8 508 50 I-26 508 38 I-13 508 47 I-27 508 40 I-16 508 32 I-33 508 30 540 42 I-20 490 27 C-4 505 32 510 30 540 17 I-21 510 64 I-5 540 91 543 88 510 71 I-23 510 41 I-11 500 84 525 78 I-24 508 46 I-15 485 30 550 41 510 36 I-31 510 24 I-19 540 >100 540 20 I-32 510 47 I-22 490 50 490 35 510 45 C-2 504 48 I-29 512 57 I-3 510 36 Dye Stain in the B&W Format (Miscellaneous. dyes) Dye λmax ODx103 Dye λmax ODx103 C-3 545 79 I-12 510 39 505 58 I-41 540 >100 I-17 515 40 I-42 490 44 I-30 510 41 515 55 C-18 510 13 I-34 510 44
Dye Speed and Stain in the Color Format Sensitization Stain lmax Speed SR lmax OD103 C-1 550 197 233 510 37 I-2 540 179 224 510 12 I-8 550 192 226 510 13 I-16 550 199 220 510 10 I-24 540 180 214 510 3 I-32 550 193 227 510 7 I-37 540 188 228 505 12 C-2 540 188 223 508 19 I-3 540 192 218 510 5 I-14 540 176 209 508 8 I-26 540 185 212 510 2 C-4 550 197 240 512 50 545 17 I-29 550 194 223 515 4 C-3 550 186 233 512 46 550 105 I-41 540 191 219 510 44 545 89 I-15 540 157 211 510 9 C-20 630 142 189 582 65 I-39 550 114 151 580 18 C-19 470 186 223 465 68 I-35 470 191 219 465 34 c-18 --- --- * --- 0 I-43 550 190 221 512 24 I-44 550 223 512 53
* Did not sensitize

The data presented in Tables III - V indicate that the dyes used according to the invention provided effective sensitization and gave significantly lower post-processing stain than the comparison dyes, particularly in the color format which contained the water-immiscible emulsion of color coupler into which the sensitizing dyes could at least partially migrate.


Anspruch[de]
  1. Photographisches Silberhalogenidelement mit einem Sensibilisierungsfarbstoff mit der Formel:
    worin
    • X1 und X2 jeweils unabhängig voneinander stehen für die Atome, die erforderlich sind, um einen Benzo-kondensierten 5- oder 6-gliedrigen heterocyclischen Kern zu vervollständigen, der zusätzlich zur Substitution durch Z1 bzw. Z2 weiter substituiert oder unsubstituiert sein kann;
    • n steht für eine positive Zahl von 1 bis 4,
    • p und q jeweils unabhängig voneinander stehen für 0 oder 1,
    • L jeweils unabhängig voneinander steht für eine substituierte oder unsubstituierte Methingruppe;
    • R1 und R2 jeweils unabhängig voneinander stehen für substituiertes oder unsubstituiertes Aryl oder substituiertes oder unsubstituiertes Alkyl,
    • Z1 steht für einen Substituenten, der sowohl eine Amidgruppe als auch einen aromatischen Ring enthält, jedoch nicht einen heterocyclischen 5-gliedrigen Ring aufweist, der mehr als ein Heteroatom aufweist, eine Hydroxyarylacylgruppe, eine Hydrazin-Derivatgruppe oder ein Ethersauerstoffatom und worin Z2 für H oder einen Substituenten steht, und worin
    • W1 ein Gegenion ist, das zum Ausgleich der Ladung des Moleküls benötigt wird.
  2. Photographisches Silberhalogenidelemept nach Anspruch 1, in dem der Farbstoff die Formel hat:
    worin
    • X1 und X2 unabhängig voneinander stehen für die Atome, die erforderlich sind, um einen Benzothiazolkern, Benzoxazolkern, Benzoselenazolkern, Benzotellurazolkern, Chinolinkern oder Benzimidazolkern zu vervollständigen, der zusätzlich zur Substitution durch Z1 bzw. Z2 weiter substituiert oder unsubstituiert sein kann,
    • n für eine positive Zahl von 1 bis 4 steht,
    • L jeweils unabhängig voneinander eine substituierte oder unsubstituierte Methingruppe darstellt,
    • Z1 für einen Substituenten steht, der sowohl eine Amidgruppe als auch einen aromatischen Ring enthält, jedoch keinen heterocyclischen 5-gliedrigen Ring aufweist, der mehr als ein Heteroatom aufweist, eine Hydroxyarylacylgruppe, eine Hydrazin-Derivatgruppe oder ein Ethersauerstoffatom und worin Z2 für H oder einen nicht-aromatischen Substituenten steht;
    • R1 und R2 jeweils unabhängig voneinander für ein substituiertes oder unsubstituiertes Aryl oder substituiertes oder unsubstituiertes Alkyl stehen; und worin
    • W1 für ein Gegenion steht, das zum Ausgleich der Ladung des Moleküls benötigt wird.
  3. Photographisches Silberhalogenidelement nach Anspruch 1 mit einem Sensibilisierungsfarbstoff mit der Formel:
    worin
    • n eine positive Zahl von 1 bis 4 ist,
    • L jeweils unabhängig voneinander steht für eine substituierte und unsubstituierte Methingruppe und worin der Benzolring eines jeden Kernes weiter substituiert oder unsubstituiert sein kann;
    • Q1 und Q2 unabhängig voneinander stehen für O, N, S oder Se;
    • R1 und R2 jeweils unabhängig voneinander für substituiertes oder unsubstituiertes Aryl oder substituiertes oder unsubstituiertes Alkyl stehen,
    • Z1 für einen Substituenten steht, der sowohl eine Amidgruppe als auch einen aromatischen Ring enthält, jedoch keinen heterocyclischen 5-gliedrigen Ring aufweist, der mehr als ein Heteroatom enthält, eine Hydroxyarylacylgruppe, eine Hydrazin-Derivatgruppe oder ein Ethersauerstoffatom und worin Z2 für H oder einen nicht-aromatischen Substituenten steht;
    • R1 und R2 jeweils unabhängig voneinander für substituiertes oder unsubstituiertes Aryl oder substituiertes oder unsubstituiertes Alkyl stehen; und worin
    • W1 ein Gegenion ist, das zum Ausgleich der Ladung des Moleküls benötigt wird.
  4. Photographisches Silberhalogenidmaterial nach Anspruch 1, in dem der Farbstoff die Formel hat:
    worin R1 und R2 für kurzkettiges Alkyl stehen, wobei mindestens eins hiervon substituiert ist durch eine Säure- oder Säuresalzgruppe, R9 kurzkettiges Alkyl ist, Z1 ein Substituent ist, der eine aromatische Gruppe und eine Amidgruppe enthält, jedoch keinen heterocyclischen 5-gliedrigen Ring, der mehr als ein Heteroatom aufweist, eine Hydroxyarylacylgruppe, eine Hydrazin-Derivatgruppe oder ein Ethersauerstoffatom und worin Z2 steht für H, substituiertes oder unsubstituiertes kurzkettiges Alkyl, substituiertes oder unsubstituiertes Alkenyl, Halogen oder Alkoxy, worin W3 ein Gegenion ist, das zum Ausgleich der Ladung des Moleküls benötigt wird, wobei das photographische Material zusätzlich eine mit Wasser unmischbare Dispersion enthält, in die der Sensibilisierungsfarbstoff mindestens teilweise wandern kann.
  5. Photographisches Element nach einem der Ansprüche 1 bis 3, das zusätzlich eine mit Wassr unmischbare Dispersion enthält, die einen Farbkuppler aufweist, in die der Sensibilisierungsfarbstoff mindestens teilweise wandern kann.
  6. Photographisches Element nach einem der Ansprüche 1 bis 5, in dem Z1 und Z2 Substituenten in der 5-Position sind.
  7. Photographisches Element nach einem der Ansprüche 1 bis 6, in dem Z1 die Formel hat: Y1-CONR3-*; Y1-NR4-CO*; R5R6N-CO-Y2-*; oder R7-CO-NR8-Y2-* worin * die Bindungsposition an X1 darstellt, Y1 und Y2 substituierte oder unsubstituierte aromatische Gruppen sind und R3, R4, R5, R6, R7 und R8 unabhängig voneinander stehen für H oder substituiertes oder unsubstituiertes kurzkettiges Alkyl mit 1 bis 6 Kohlenstoffatomen.
  8. Photographisches Element nach einem der Ansprüche 1 bis 6, in dem Y1 ein substituierter oder unsubstituierter Benzol-, Furan-, Pyrrol- oder Thiophenring ist, worin Y2 ein substituierter oder unsubstituierter Benzolring ist.
  9. Photographisches Element nach einem der Ansprüche 1 bis 6, in dem sowohl R1 als auch R2 substituiert sind durch eine Säure- oder Säuresalzgruppe.
  10. Farbstoff mit der Formel:
    worin
    • X1 und X2 jeweils unabhängig voneinander stehen für die Atome, die erforderlich sind zur Vervollständigung eines Benzo-kondensierten 5- oder 6-gliedrigen heterocyclischen Kernes, der zusätzlich zur Substitution durch Z1 bzw. Z2 weiter substituiert oder unsubstituiert sein kann;
    • n eine positive Zahl von 1 bis 4 ist,
    • p und q jeweils unabhängig voneinander stehen für 0 oder 1,
    • L jeweils unabhängig voneinander steht für eine substituierte oder unsubstituierte Methingruppe;
    • R1 und R2 jeweils voneinander stehen für substituiertes oder unsubstituiertes Aryl oder substituiertes oder unsubstituiertes Alkyl,
    • Z1 steht für einen Substituenten, der sowohl eine Amidgruppe als auch einen aromatischen Ring enthält, jedoch keinen heterocyclischen 5-gliedrigen Ring aufweist, der mehr als ein Heteroatom enthält, eine Hydroxyarylacylgruppe, eine Hydrazin-Derivat-gruppe oder ein Ethersauerstoffatom und worin Z2 steht für H oder einen Substituenten; und worin
    • W1 ein Gegenion ist, das zum Ausgleich der Ladung des Moleküls benötigt wird.
Anspruch[en]
  1. A silver halide photographic element comprising a sensitizing dye having the formula:
    • X1 and X2 each independently represent the atoms necessary to complete a benzo-condensed 5- or 6-membered heterocyclic nucleus, which, in addition to being substituted by Z1 and Z2 respectively, may be further substituted or unsubstituted;
    • n is a positive integer from 1 to 4,
    • p and q each independently represents 0 or 1,
    • each L independently represents a substituted or unsubstituted methine group;
    • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl,
    • Z1 represents a substituent which contains both an amide group and an aromatic ring but does not contain a heterocyclic 5-membered ring which has more than one heteroatom, a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, and Z2 represents H or a substituent,
    • W1 is a counterion as needed to balance the charge of the molecule.
  2. A silver halide photographic element according to claim 1, wherein the dye has the formula:
    • X1 and X2 independently represent the atoms necessary to complete a benzothiazole nucleus, benzoxazole nucleus, benzoselenazole nucleus, benzotellurazole nucleus, quinoline nucleus or benzimidazole nucleus, which, in addition to being substituted by Z1 and Z2 respectively, may be further substituted or unsubstituted,
    • n is a positive integer from 1 to 4,
    • each L independently represents a substituted or unsubstituted methine group,
    • Z1 represents a substituent which contains both an amide group and an aromatic ring, but does not contain a heterocyclic 5-membered ring which has more than one heteroatom, a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, and Z2 represents H or a non-aromatic substituent;
    • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl;
    • W1 is a counterion as needed to balance the charge of the molecule.
  3. A silver halide photographic element according to claim 1 comprising a sensitizing dye having the formula:
    • n is a positive integer from 1 to 4,
    • each L independently represents a substituted or unsubstituted methine group, and the benzene ring of each nucleus may be further substituted or unsubstituted;
    • Q1 and Q2 are, independently, O, N, S or Se;
    • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl,
    • Z1 represents a substituent which contains both an amide group and an aromatic ring but does not contain a heterocyclic 5-membered ring which has more than one heteroatom, a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, and Z2 represents H or a non-aromatic substituent;
    • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl;
    • W1 is a counterion as needed to balance the charge of the molecule,
  4. A silver halide photographic material according to claim 1, wherein the dye has the formula:
    wherein R1 and R2 represent lower alkyl at least one of which is substituted with an acid or acid salt group, R9 is a lower alkyl, Z1 is a substituent that contains an aromatic group and an amide group, but does not contain a heterocyclic 5-membered ring which has more than one heteroatom, a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, Z2 is H, substituted or unsubstituted lower alkyl, substituted or unsubstituted alkenyl, halogen, or alkoxy, W3 is a counterion as needed to balance the charge of the molecule the photographic material additionally comprising a water-immiscible dispersion into which said sensitizing dye can at least partially migrate.
  5. A photographic element according to any of claims 1 to 3 additionally comprising a water-immiscible dispersion carrying a color coupler, into which said sensitizing dye can at least partially migrate.
  6. A photographic element according to any of claims 1 to 5 wherein Z1 and Z2 are 5-position substituents.
  7. A photographic element according to any of claims 1 to 6, wherein Z1 has the formula: Y1-CONR3-*; Y1-NR4-CO-*; R5R6N-CO-Y2-; or R7-CO-NR8-Y2-* wherein * represents the bonding position to X1, Y1 and Y2 are substituted or unsubstituted aromatic groups and R3, R4, R5, R6, R7 and R8 are independently H or substituted or unsubstituted lower alkyl of 1 to 6 carbon atoms.
  8. A photographic element according to any of claims 1 to 6 wherein Y1 is a substituted or unsubstituted benzene, furan, pyrrole or thiophene ring and Y2 is a substituted or unsubstituted benzene ring.
  9. A photographic element according to any one of claims 1 to 6 wherein both of R1 and R2 are substituted with an acid or acid salt group.
  10. A dye having the formula:
    • X1 and X2 each independently represent the atoms necessary to complete a benzo-condensed 5- or 6-membered heterocyclic nucleus, which, in addition to being substituted by Z1 and Z2 respectively, may be further substituted or unsubstituted;
    • n is a positive integer from 1 to 4,
    • p and q each independently represents 0 or 1,
    • each L independently represents a substituted or unsubstituted methine group;
    • R1 and R2 each independently represents substituted or unsubstituted aryl or substituted or unsubstituted alkyl,
    • Z1 represents a substituent which contains both an amide group and an aromatic ring but does not contain a heterocyclic 5-membered ring which has more than one heteroatom, a hydroxyarylacyl group, a hydrazine-derivative group or an ether oxygen atom, and Z2 represents H or a substituent;
    • W1 is a counterion as needed to balance the charge of the molecule.
Anspruch[fr]
  1. Elément photographique aux halogénures d'argent comprenant un colorant sensibilisateur ayant la formule :
    • X1 et X2 représentent chacun séparément les atomes nécessaires pour compléter un noyau benzo-hétérocyclique condensé avec un hétérocycle à 5 ou 6 membres qui, en plus d'être substitué par Z1 et Z2 respectivement, peut être substitué davantage ou non ;
    • n est un nombre entier positif compris entre 1 et 4 ;
    • p et q représentent chacun séparément 0 ou 1 ;
    • chaque groupe L représente séparément un groupe méthinique substitué ou non ;
    • R1 et R2 représentent chacun séparément un groupe aryle substitué ou non ou un groupe alkyle substitué ou non ;
    • Z1 représente un substituant qui contient à la fois un groupe amide et un noyau aromatique, mais qui ne contient pas d'hétérocycle à 5 membres ayant plus d'un hétéroatome, un groupe hydroxyarylacyle, un groupe dérivé de l'hydrazine ou l'atome d'oxygène d'un éther, et Z2 représente H ou un substituant ;
    • W1 est un ion complémentaire requis pour équilibrer la charge de la molécule.
  2. Elément photographique aux halogénures d'argent selon la revendication 1, dans lequel le colorant a la formule :
    • X1 et X2 représentent séparément les atomes nécessaires pour compléter un noyau benzothiazole, un noyau benzoxazole, un noyau benzosélénazole, un noyau benzotellurazole, un noyau quinoléine ou un noyau benzimidazole, qui, en plus d'être substitué par Z1 et Z2 respectivement, peut être substitué davantage ou non ;
    • n est un nombre entier positif compris entre 1 et 4 ;
    • chaque groupe L représente séparément un groupe méthinique substitué ou non ;
    • Z1 représente un substituant qui contient à la fois un groupe amide et un noyau aromatique, mais qui ne contient pas d'hétérocycle à 5 membres ayant plus d'un hétéroatome, un groupe hydroxyarylacyle, un groupe dérivé de l'hydrazine ou l'atome d'oxygène d'un éther, et Z2 représente H ou un substituant non aromatique ;
    • R1 et R2 représentent chacun séparément un groupe aryle substitué ou non ou un groupe alkyle substitué ou non ;
    • W1 est un ion complémentaire requis pour équilibrer la charge de la molécule.
  3. Elément photographique aux halogénures d'argent selon la revendication 1, comprenant un colorant sensibilisateur ayant la formule :
    • n est un nombre entier positif compris entre 1 et 4 ;
    • chaque groupe L représente séparément un groupe méthinique substitué ou non, et le cycle benzénique de chaque noyau peut être substitué davantage ou non ;
    • Q1 et Q2 représentent séparément O, N, S ou Sè ;
    • R1 et R2 représentent chacun séparément un groupe aryle substitué ou non ou un groupe alkyle substitué ou non ;
    • Z1 représente un substituant qui contient à la fois un groupe amide et un noyau aromatique, mais qui ne contient pas d'hétérocycle à 5 membres ayant plus d'un hétéroatome, un groupe hydroxyarylacyle, un groupe dérivé de l'hydrazine ou l'atome d'oxygène d'un éther, et Z2 représente H ou un substituant non aromatique ;
    • R1 et R2 représentent chacun séparément un groupe aryle substitué ou non ou un groupe alkyle substitué ou non ;
    • W1 est un ion complémentaire requis pour équilibrer la charge de la molécule.
  4. Elément photographique aux halogénures d'argent selon la revendication 1, dans lequel le colorant a la formule :
    dans laquelle R1 et R2 représentent un groupe alkyle inférieur, au moins l'un d'entre eux étant substitué par un groupe acide ou sel d'acide ; R9 représente un groupe alkyle inférieur ; Z1 est un substituant qui contient un groupe aromatique et un groupe amide, mais ne contient pas d'hétérocycle à 5 membres ayant plus d'un hétéroatome, un groupe hydroxyarylacyle, un groupe dérivé de l'hydrazine ou l'atome d'oxygène d'un éther ; Z2 représente H, un groupe alkyle inférieur substitué ou non, un groupe alcényle substitué ou non, un halogène ou un groupe alkoxy ; W3 est un ion complémentaire requis pour équilibrer la charge de la molécule, l'élément photographique comprenant de plus une dispersion non miscible à l'eau dans laquelle ledit colorant sensibilisateur peut migrer, au moins partiellement.
  5. Elément photographique selon l'une quelconque des revendications 1 à 3, comprenant de plus une dispersion non miscible à l'eau transport un coupleur chromogène, dans laquelle ledit colorant sensibilisateur peut migrer, au moins partiellement.
  6. Elément photographique selon l'une quelconque des revendications 1 à 5, dans lequel Z1 et Z2 sont des substituants en position 5.
  7. Elément photographique selon l'une quelconque des revendications 1 à 6, dans lequel Z1 a la formule : Y1-CONR3-*; Y1-NR4-CO-*; R5R6N-CO-Y2*; ou R7-CO-NR8-Y2-* dans laquelle * représente la position de liaison à X1 ; Y1 et Y2 sont des groupes aromatiques substitués ou non ; et R3, R4, R5, R6, R7 et R8 représentent séparément H ou un groupe alkyle inférieur substitué ou non, ayant 1 à 6 atomes de carbone.
  8. Elément photographique selon l'une quelconque des revendications 1 à 6, dans lequel Y1 est un noyau benzène, furane, pyrrole ou thiophène, substitué ou non, et Y2 est un noyau benzénique substitué ou non.
  9. Elément photographique selon l'une quelconque des revendications 1 à 6, dans lequel R1 et R2 sont tous deux substitués par un groupe acide ou sel d'acide.
  10. Colorant ayant la formule :
    • X1 et X2 représentent chacun séparément les atomes nécessaires pour compléter un radical benzo-hétérocyclique condensé à 5 ou 6 membres qui, en plus d'être substitué par Z1 et Z2 respectivement, peut être substitué davantage ou non ;
    • n est un nombre entier positif compris entre 1 et 4 ;
    • p et q représentent chacun séparément 0 ou 1 ;
    • chaque groupe L représente séparément un groupe méthinique substitué ou non ;
    • R1 et R2 représentent chacun séparément un groupe aryle substitué ou non ou un groupe alkyle substitué ou non ;
    • Z1 représente un substituant qui contient à la fois un groupe amide et un noyau aromatique, mais qui ne contient pas d'hétérocycle à 5 membres ayant plus d'un hétéroatome, un groupe hydroxyarylacyle, un groupe dérivé de l'hydrazine ou l'atome d'oxygène d'un éther; et Z2 représente H ou un substituant ;
    • W1 est un ion complémentaire requis pour équilibrer la charge de la molécule.






IPC
A Täglicher Lebensbedarf
B Arbeitsverfahren; Transportieren
C Chemie; Hüttenwesen
D Textilien; Papier
E Bauwesen; Erdbohren; Bergbau
F Maschinenbau; Beleuchtung; Heizung; Waffen; Sprengen
G Physik
H Elektrotechnik

Anmelder
Datum

Patentrecherche

Patent Zeichnungen (PDF)

Copyright © 2008 Patent-De Alle Rechte vorbehalten. eMail: info@patent-de.com