Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0075—Preparations with cationic dyes

Definitions

• D represents a divalent aromatic group combining with each other the pyromidinylamino groups or triazinylamino groups shown in the above formula
• R R R and R each represents a hydrogen atom, a
• hydroxyl group an alkoxyl group, a halogen atom, an amino group, an alkyl amino group or a substituted alkylamino group, such as, a hydroxyalkylamino group, a sulfoalkylamino group, a cycloalkylamino group, an arylamino group and a heterocyclic amino residual group, and
• W represents CH- or N-.
• the present invention relates generally to a spectrally sensitized photographic silver halide emulsion and more part icularly to a spectrally sensitized photographic silver halide emulsion in which the formation of photographic fog has been suppressed and the reduction of the spectral sensitivity during long storage has been prevented.
• the intensity of the spectral sensitization is influenced not only by the chemical stnlcture of the sensitizing dye, thepropertiesofthe emulsion, such as, the composition of the silver halide, the crystal structure of the silver halide, the concentration of silver ions in the emulsion, the pH of the emulsion and the like, but also by the kinds of stabilizers, wetting agents, hardening agents, and couplers present together in the emulsion. In most cases, these compounds incorporated in the silver halide emulsion other than the sensitizing dye are apt to reduce the spectral sensitization.
• a sensitizing dye is able to sensitize spectrally the emulsion when added to the emulsion
• the addition thereof to the silver halide emulsion is usually accompanied with certain faults such as the formation of fog, the reduction of the property of keeping spectral sensitivity and the like. Therefore, in order to prepare a photographic silver halide lightsensitive element showing less fog and having a good keeping property, it is highly necessary to inhibit the formation of fog caused by the addition of a sensitizing dye and improve the reduction of the spectral sensitivity, which occurs during the long storage.
• an object of the present invention is to provide a photographic silver halide emulsion which has been spectrally sensitized and in which the formation of fogging by dyes and also the deterioration in the spectrally sensitizing property of the dye, in the course of storage, have been prevented without reducing substantially the spectral sensitivity itself.
• X is an acid anion group
• m l or 2
• p is l or 2
• said dye forming an intramolecular salt when p is l, and together with a compound having triazine nuclei or pyrimidine nuclei represented by the following general wherein D represents a divalent aromatic group combining with each other the pyromidinylamino groups or triazinylamino groups shown in the above formula.
• R,, R, R and R each represents a hydrogen atom, 5 hydroxyl group, an alkoxyl group, a halogen atom, an amino group, an alkyl amino group, a substituted alkylamino group, such as, a hydroxyalkylamino group, a sulfoalkylamino group, a cycloalkylamino group, an arylamino group and a heterocyclic amino residual group, and
• Z may be 4-quinolinc nuclei having a substituent, such as, a halogen atom, an alkyl group, an alkoxyl group and the like.
• Z is a nonmetallic atomic group necessary for forming a heterocyclic nucleus, such as, a 4- quinoline nucleus, a Z-quinoline nucleus, a naphthothiazole nucleus, a napthoselenazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a benzoxazole nucleus, a thiazole nucleus, an oxazole nucleus, and the like.
• R, and R may be a lower alkyl group, such as, a methyl group, an ethyl group and a propyl group; substituted alkyl group, such as, B-hydroxyethyl group, a B-acctoxyethyl group, an ethylsulfate group; and the like; a carboxylalkyl group or a derivative thereof such as, a carboxyethyl group, a 2-(2-carboxyethoxy)ethyl group and the like; or a sulfoalkyl group and a derivative thereof, such as, a B-sulfoethyl group, a -y-sulfopropyl group, a 2-hydroxy-l-sulfopropyl group, a 3- methoxy-2-(3-sulfopropoxy)propyl group and the like.
• the sensitizing dye in this invention is that the dye includes at least one quinoline hetero nucleus.
• D may be any divalent atomic group which combines the pyrimidinylamino nuclei each other or the triazinylamino nuclei each other in the above-mentioned formula I], such as, a biphenylene group, a phenylene group, a naphthylene group, a stilbene group, a bibenzyl I group and the derivatives thereof.
• the feature of the compound shown in general formula II is in a point that the compound has the pyrimidinylamino nuclei or the triazinylamino nuclei bridged to each other by the aforesaid atomic group D.
• the sensitizing dye represented by general formula I can sensitize spectrally in a region from a green to red arbitrarily by selecting two heterocyclic nuclei.
• the sensitizing dye used in this invention can spectrally sensitize a silver halide emulsion stronger than the case of using a dye having no quinoline nucleus.
• the sensitizing dye is a trirnethine cyanine dye, it can strongly sensitize spectrally a silver halide emulsion even up to the red region which can be attained by using a pentamethine cyanine dye.
• sensitizing dyes used in the present invention show M- band type spectral sensitization and such spectral distribution is quite suitable to use in a red-sensitive emulsion layer.
• faults such as, fog caused by the dye is easily formed and the spectral sensitivity obtained tends to be lowered in the course of storage.
• the sensitizing dye shown by general formula I when the sensitizing dye shown by general formula I is incorporated in a silver halide emulsion layer along with the compound shown by general formula II having substantially no absorption in a visible region and having a strong absorption in a near ultraviolet region, the formation of fog by the dye can effectively be inhibited and the reduction in spectral sensitivity in the course 3 4 of storage can be almost completely prevented without sub- (ID) stantially reducing the spectral sensitivity itself. That is, the S compound shown by general formula II not only prevents the reduction of the spectrally sensitizing property of such a J trimethincyanine dye showing M-band type spectral sensitiza- 5 l tion but also markedly increase the spectral sensitivity.
• the sensitizing dye shown by N l Id h general formula I along with the compound shown by general formula ll, the color stain formed by the sensitizing dye after photographic processing is reduced and also the harmful action of co pler present therewith on the spectral sensitization N -l( W is less.
• the compound shown by general formula I and the com J k/ pound shown by general formula II may be incorporated into a silver halide emulsion separately or together as a solution in a water-soluble organic solvent such as, methanol, ethanol, or alkaline methanol, or as an aqueous solution.
• a water-soluble organic solvent such as, methanol, ethanol, or alkaline methanol
• N be controlled according to the properties of these compounds, NHU NH CHTCH' the properties of the emulsion, the kinds of additives to be N I ⁇ I added to the silver halide emulsion together with the dyes and a the like. They may be used in various ratios.
• the silver halide used in the silver halide emulsion may be silver iodobromide, silver chlorobromide, silver chloride and the like.
• the silver halide emulsion of this invention may he prepared in a conventional manner and may be applied to a g g l N I proper support, such as, a film of a cellulose derivative, a
• sensitizing dyes shown by general formula I and ll are shown below, but it should be understood Q that the sensitizing dye used in this invention is not limited to them only.
• the compound wherein W in said forsensitizing supersensi mula is N that is, the compound having an s-triazine may y fi r, ml. 1 be prepared by a known method.
• the unrcacted amine was removed by extracting with benzene ID 3 11d 0a 500 11:01 and the solvent of dimethylformamide and water was removed 9 IE 0 nd H 100 0 u m from the system by distillation under a reduced pressure.
• IE 1 11d 100 100 0. 05
• 20 g. of the residue prepared above was heated for 3 g hours under refluxing in 100 ml. of aniline and the reaction IE ⁇ 1 Mb 2 79 17s 0.011 product mixture was added to about 250 ml.
• iodobromide emulsion prepared by a conventional method which contains Ag X by 33x10" mols, and furthermore, a EXAMPLEZ methanol solution of l l0' mols of the compound shown by To 100 of a silver chlorobmmide emulsion re med b a general formula ll was immediately added in the amount conventioil method which contains g x y 2 i Show in i The emulsiim thus prepare!
• R;,, R R and R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atoms, an amino group, an alkyl amino group, a substituted alkylamino group, an arylamino group, and heterocyclic amino residual group, and
• D represents an aromatic divalent atomic group bonding to each other the pyrimidinylamino nuclei or the traizinylamino nuclei shown in Formula B.
• the heterocyclic nucleus completed by Z is selected from the group consisting of a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a napthoxazole nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a benzoxazole nucleus, a thiazole nucleus and an oxazole nucleus; and the aromatic divalent atomic group represented by D is selected from the group consisting of 4.
• a photographic light sensitive element comprising a sup port having thereon at least one layer containing a photographic silver halide emulsion as claimed in claim I.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

Applications Claiming Priority (1)

Publications (1)

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ID=13484211

Family Applications (1)

Country Status (5)

Cited By (12)

Families Citing this family (1)

• 1967
  • 1967-10-31 GB GB49494/67A patent/GB1209755A/en not_active Expired
  • 1967-11-02 DE DE19671597586 patent/DE1597586A1/de active Pending
  • 1967-11-02 CH CH1536467A patent/CH484448A/de not_active IP Right Cessation
  • 1967-11-02 US US680024A patent/US3615641A/en not_active Expired - Lifetime
  • 1967-11-02 FR FR1603339D patent/FR1603339A/fr not_active Expired

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