Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/18—One oxygen or sulfur atom
  • C07D231/20—One oxygen atom attached in position 3 or 5
  • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds

Definitions

• a light-sensitive silver halide emulsion layer on a negative is exposed, and generally contacted with a receiving or positive material in the presence of a developer.
• development nuclei are provided to promote development, these nuclei being material such as the sulphides of the heavy metals, fogged silver halides, etc.
• the present invention provides a process involving the same general area of the art as the abovediscussed references, but which provides a unique combination for liberating reactive materials during processing.
• the present invention provides a novel photographic negative element for use in a diffusion transfer process which comprises a support having thereon a silver halide emulsion layer containing a coupler dissolved in a high boiling organic solvent and a color developing agent, said coupler being insoluble in water but soluble in an alkaline medium and said organic solvent being immiscible with water but miscible with an alkaline medium.
• a novel photographic negative element for use in a diffusion transfer process which comprises a support having thereon a silver halide emulsion layer containing a coupler dissolved in a high boiling organic solvent and a color developing agent, said coupler being insoluble in water but soluble in an alkaline medium and said organic solvent being immiscible with water but miscible with an alkaline medium.
• a novel color diffusion process comprising exposing a photographic negative material having a silver halide emulsion layer containing a coupler dissolved in a high boiling organic solvent and a color developing agent, said coupler being insoluble in water but soluble in an alkaline medium, said organic solvent being immiscible with water but miscible with an alkaline medium; processing, in an alkaline processing solution, said negative material being in close contact with a photographic positive material having an image-receiving layer containing an oxidizing agent, said developing agent being thereby consumed by the reaction with silver halide in the exposed areas of said emulsion layer, whereas silver halide, coupler and developing agent in the non-exposed areas thereof are diffusion-transferred to said image-receiving layer by the action of said processing solution to form a color image in said image-receiving layer, and thereafter removing said positive material from said negative material.
• One object of the present invention is to provide a novel transfer material useful in the color photographic diffusion transfer process.
• the negative material used in the present invention is composed of a support having thereon an emulsion layer containing light-sensitive silver halide grains, a color developing agent and a specific coupler (which Will be described below in detail) dispersed in a high boiling organic solvent (which will also be explained below).
• the positive material used in the present invention is composed of a support having thereon an image receiving layer containing an oxidizing agent, such as a fogged silver halide emulsion, chloranil or an active clay.
• an oxidizing agent such as a fogged silver halide emulsion, chloranil or an active clay.
• the negative material After exposing the negative material to active radiation, the negative material is placed on the positive material so that the exposed emulsion layer of the negative material faces the image-receiving layer of the positive material. This is then immersed in aqueous alkali (as in the conventional silver salt diffusion transfer process), or else, aqueous alkali is inserted between the emulsion layer of the negative material and the image-receiving layer of the positive material by some other suitable manner, such as by using a commercially available processer for the silver salt diffusion transfer process, whereby the aqueous alkali* diffuses into the negative emulsion layer to dissolve the high boiling organic sol-vent.
• the coupler dispersed in the high boiling organic solvent thus becomes ready to react.
• the color developing agent develops the exposed silver halide grains and suffers oxidation.
• the oxidation products of the color developing agents which are thus formed give rise to the coupling reaction (color formation) with the couplers in the layer, and a non-difiusible dye deposits in situ.
• the invention has merits such as the negative material has good preservability or stability since the coupler is protected in an oily packet in the negative emulsion layer. Also, the transfer process can be readily conducted.
• the coupler used in this invention is not diffusible in a neutral aqueous solution and becomes diffusible only in alkaline media. It is, however, soluble in the organic solvents later discussed. Moreover, the coupler used in this invention can react with the oxidation product of the color developing agent to form a dye.
• Typical examples of the couplers used in the present invention are as follows:
• a coupler containing a chromogenic nucleus such as phenol, naphthol, pyrazolone, and fi-keto acid anilide can be used.
• a chromogenic nucleus such as phenol, naphthol, pyrazolone, and fi-keto acid anilide.
• color developing agent used in the present invention there can be given, as illustrative, N,N-dialkyl-pphenylenediamine derivatives which are usually used in color photographic process.
• the following well-known compounds can be used as the color developing agent in the present invention:
• the aforesaid components may either be added directly to the silver halide emulsion or be dissolved in the coupled solvent together with the coupler and then dispersed as fine particles in the silver halide emulsion.
• the coupler When the coupler is incorporated in a silver halide photographic emulsion according to conventional preparation processes for color photographic light-sensitive materials, c.g., by dissolving the coupler in a high 'boiling solvent such as dibutyl phthalate or tricresyl phosphate and dispersing the solution in a silver halide emulsion, the expected color density cannot be obtained. The reason is 'believed to be that since the coupler is present in the oil droplet, the coupler cannot be brought sufliciently into contact with the aqueous alkaline phase during processing.
• a high 'boiling solvent such as dibutyl phthalate or tricresyl phosphate
• the coupler solvent a non volatile solvent which is poorly soluble in water but which becomes soluble in an aqueous alkaline medium is employed as the coupler solvent.
• the coupler can easily be dissolved out and diffused into the image-receiving layer to provide therein a transferred image having sufficient color density.
• R100 X wherein X represents hydrogen or a methyl group, R and R each represent an unsubstituted or a substituted alkyl group, the sum of the number of carbon atoms in groups R and R being an integer from 7 to 11.
• Specific examples of such solvents are as follows:
• the mixture was heated for one hour on a hot water bath and then distilled under reduced pressure to provide 170 g. of a fraction at 91 C./1 mm. Hg.
• the fraction was reacted with 92 g. of freshly distilled acetic anhydride as in the case of preparing Compound 9 and the product was again distilled under reduced pressure to provide 180 'g. of a fraction at -145 C./1 mm. Hg.
• the product was then mixed with 500 ml. of an aqueous 2 N sodium hydroxide solution containing 50 ml. of methanol and subjected to hydrolysis by shaking the mixture, whereby the liquid became transparent.
• the solution was then acidified with hydrochloric acid and the oily material that separated was extracted with ether, washed with water, dried, and freed from the solvent by evaporation in vacuo to provide g. of Compound 11.
• Example 5 it is also possible (as shown in Example 5) to transfer multiple-color copy by using a multi-layer color photographic lightsensitive material having photographic emulsion layers which each contains a coupler providing a different color hue and which each have a different spectral sensitivity.
• the solvent used for dispersing the coupler in a silver halide emulsion in the present invention need not necessarily be of a single composition, but may be a mixture with a solubilizable amount of an alkali-insoluble solvent.
• the oxidizing agent contained in the image-receiving layer of the positive material of the present invention is one which is capable of oxidizing the color developing agent to quinonediimine.
• Chloranil or active clay is dispersed in a medium such as gelatin or latex and the dispersion is applied to a support.
• a silver halide emulsion which has been fogged by chemicals or by light is partic ularly excellent with regard to color density.
• metallic silver is formed together with a dye image, and hence the former has to be removed in a bleach-fixing or a bleach-stabilizing bath.
• the alkaline solution used in the transfer process must have a concentration sufficient to dissolve the solvent and the coupler to such an extent that they diffuse into the image-receiving layer. A concentration of about 1 N gives best results.
• sodium carboxymethyl cellulose can be added to the alkaline solution.
• Example 4 by applying a silver halide emulsion layer which has not been fogged to the surface of the negative material, the formation of transfer fog on the image-receiving layer corresponding to the exposed portion of the negative material can be prev ented.
• the primary feature of the present invention is in that the couplers and the color developing agents in the unexposed portions of the negative material diffuse into the image-receiving layer of the positive material, where the coupler causes the coupling reaction with the aid of the oxidizing agents present in the imagereceiving layer.
• This purpose is achieved by dispersing the coupler which is insoluble in water but soluble in an alkaline solution in the silver halide emulsion for the negative material using a coupler solvent which is insoluble in water but soluble in an alkaline medium.
• EXAMPLE 1 In 2.1 ml. of ethyl acetate were dissolved 0.9 g. of a cyan forming coupler, N-(Z-ethylhexyl)-1-hydroxy-2- naphthamide (Compound 2) and 2.1 g. of a color developing agent, 3 methyl 4 amino- [N-ethyl-N-(methanesulfonamido)ethyl]-aniline (Compound 8), and the resulting solution was uniformly mixed with 1.1 g. of 3-[N- (2 ethylhexyl)acetamido] propionic acid (Compound 11). The mixture was added to 52 ml. of a 10% gelatin solution containing a surface active agent with mechanical stirring to disperse it into the colloidal state.
• the positive material was prepared by applying a composition consisting of 100 ml. of an aqueous 5% gelatin solution and 0.5 g. of chloranil to a paper followed by drying.
• the negative material prepared above was exposed through a negative and immersed for 5 seconds at 25 C. in an activator of the following composition:
• Sodium hydroxide 40 g. Water to make 1 liter
• the emulsion layer of the negative material having the activator thereon was brought into close contact with the image-receiving layer of the positive material prepared above and they were squeezed together by passing them through a pair of rollers. After 20 seconds, the positive material was separated from the negative material to obtain a cyan color image at the portions of the image-receiving layer corresponding to the unexposed portions of the emulsion layer of the negative material.
• EXAMPLE 2 In 5 ml. of methanol was dissolved 2.5 g. of a magenta coupler, 1 phenyl 3 nonyl 5 pyrazolone (Compound 4) and then the solution was mixed with 2.5 g. of a color developing agent, 3 methyl 4 amino- N,N-diethylaniline (Compound 7) and 2.6 g. of a dispersing solvent, 2 methyl 3 [N (2 ethylhexyl)- butyramido]-propionic acid (Compound 10). The resulting solution was colloidally dispersed in 50 ml. of an aqueous 10% gelatin solution with mechanical stirring.
• the dispersion thus obtained was added to 100 g. of a silver halide photographic emulsion containing 2.9 g. of silver chloride and 7.45 g. of gelatin, and after adding suitable amounts of additives, the emulsion was applied to a baryta paper to yield a layer containing 1.7 g. of the silver halide per 1 m? of said layer, and dried.
• the negative material prepared above was exposed through a negative and immersed for 10 seconds in an activator of the following composition:
• Sodium hydroxide 32 g. Water to make 1 liter
• the emulsion layer of the negative material having the activator thereon was closely brought into contact with the image-receiving layer of the positive material and they were squeezed by passing them in the superposed state through a pair of rollers.
• EXAMPLE 3 The negative material prepared by the same procedure as m Example 1 was exposed through a negative, the emulslon layer of the negative material was brought into close contact with the image-receiving layer of a positive material which was prepared by applying a silver chloride emulsion, sufliciently fogged by light, to a support. The assembly was immersed in an activator of the following composition:
• Sodium hydroxide 40 g. Water to make 1 liter at 25 C. and thereafter squeezed by passing the superposed assembly through a pair of rollers.
• the positive material was stripped from the negative material, immersed for 2 seconds in a stopping solution consisting of an aqueous 1.5% acetic acid solution, and processed for seconds at C. in a bleach-stabilizing solution of the following composition to provide a cyan color image on the positive material:
• EXAMPLE 4 In 1.5 ml. of cyclohexane there was dissolved a magenta coupler, l phenyl 3 pentyl 5 pyrazolone (Compound 3) and the resulting solution was well mixed with 6.3 g. of a dispersing solvent, 2 methyl 3 (N noctylacetamido)-propionic acid (Compound 9). The solution was dispersed in 50 ml. of an aqueous 10% gelatin solution containing a color developing agent, N,N-diethyl-p-phenylenediamine (Compound 6) with mechanical stirring.
• a magenta coupler l phenyl 3 pentyl 5 pyrazolone
• Compound 9 2 methyl 3 (N noctylacetamido)-propionic acid
• the dispersion was added to 100 g. of a gelatino silver chlorobromide emulsion containing 50 mole percent silver bromide, and after adding suitable amounts of standard photographic additives, the resulting emulsion was applied to a baryta paper to yield a coated emulsion layer containing 1.5 g. of the silver chlorobromide per 1 m. of the layer. This was then dried. Onto the emulsion layer thus formed was applied a gelatino silver iodobromide emulsion containing 10 mole percent silver iodide and suitable amounts of additives such as a hardening agent, a wetting agent, etc., so that the layer contained 0.6 g. of the silver iodobromido per 1 m3 thereof.
• the emulsion layer of the negative material prepared above was exposed through a negative and closely brought into contact with the image-receiving layer of a positive material prepared by applying a fogged gelatino silver chloride emulsion to a paper in an activator having the following composition:
• Sodium hydroxide 40 g. Water to make 1 liter The assembly in a superposed state was squeezed by passing it through a pair of rollers.
• the positive material was stripped from the negative material, immersed for 5 seconds in a stopping solution consisting of aqueous 1.5% acetic acid, and then processed for 1 minute in a bleach-fixing solution of the following composition:
• Crystalline sodium thiosulfate 220.0 g. Potassium thiocyanate: 8.5 g. Water to make 1 liter The image-receiving layer was then washed with running water for 30 minutes to provide a magenta color image on the image-receiving layer of the positive material corresponding to the unexposed areas of the emulsion layer of the negative material. Also, no transfer fogs were observed at the image-receiving layer corresponding to the exposed portion of the emulsion layer of the negative material.
• Emulsion I Emulsion I
• a gelatin solution Emulsion II
• Emulsion II Emulsion II
• Emulsion I green-sensitive emulsion
• a cyan forming coupler N heptyl 1 hydroxy 2- naphthamide
• Compound 10 2 methyl 3 [N- (2 ethylhexyl)butyramido] propionic acid
• the mixture was then dispersed in a colloidal state with mechanical stirring in 50 ml. of an aqueous 10% gelatin solution containing 3.0 g. of a color developing agent, N,N-diethyl-p-phenylenediamine (Compound 6) and a surface active agent.
• This dispersion was then added to 1 00 g. of a gelatino silver chloride emulsion provided with a green sensitivity by a sensitizing dye with suitable amounts of additives to provide Emulsion I.
• Gelatin solution for filter layer
• a mixture of 10 g. gelatin, 0.1 g. of a dye, Zapon Fast Yellow CGR (made by Farbwerk Hoechst A.G.; Color Index 2nd ed., C.I. Solvent Yellow 69), and suitable amounts of a hardening agent and a wetting agent were dissolved in 200 ml. of water. This comprised the filter layer material.
• Emulsion II blue-sensitive emulsion
• ethyl acetate 1.5 g. of a yellow forming coupler, 2-butoxy-benzoylacetanilide (Compound 5) and the resulting solution was well mixed with 2.0 g. of a dispersing solvent, 2-methyl-3-[N-(2- ethylhexyDbutyramido]propionic acid (Compound 10).
• the solution was dispersed with mechanical stirring in 50 ml. of an aqueous 10% gelatin solution containing 3.0 g. of a color developing agent, N,N-diethyl-p'-phenylenediamine (Compound 6), 0.3 g. of a developing accelerator, l-phenyl-3-pyrazolidone, and a surface active agent.
• the dispersion was added to g. of a gelatino silver chloride emulsion provided with blue sensitivity together with suitable amounts of a hardening agent and a wetting agent to provide Emulsion II.
• a photographic negative material for use in a diffusion transfer process which comprises:
• a support having thereon a silver halide emulsion layer comprising a coupler which contains a chromogenic nucleus selected from the group consisting of phenol, naphthol, pyrazolone and ,B-ketoacid anilide dissolved in a high boiling organic solvent having the formula:
• said coupler is a member selected from the group consisting of N-heptyl-1-hydroxyl-2-naphthamide, N-(2- ethylhexyl)-l-hydroxy-Z-naphthamide, 1-phenyl-3-pentyl- '5-pyrazolone, 1-phenyl-2-nonyl-5-pyrazolone, and 2'-bu toxy-benzoylacetanilide.
• organic solvent is a member selected from the group consisting of 2-methyl-3-(N-n-octylacetamido) propionic acid, 2-methyl-3- [N- (Q-ethylhexyl)butyramido] propionic acid, and 3-[N-(2-ethylhexyl)acetamido]-propionic acid.
• said color developing agent is a member selected from the group consisting of N,N-diethyl-p-phenylenediamine, 3-methyl-4-amino-N,N-diethylaniline, and 3-methyl-4-amino-[N-ethyl-N-(2 (methanesulfoamido)ethyl]- aniline.
• a photographic negative material for use in a diffusion transfer process which comprises:
• a support having thereon, a silver halide emulsion layer comprising a coupler containing a chromogenic nucleus selected from the group consisting of phenol, naphthol, pyrazolone and fi keto acid anilide dissolved in a high boiling organic solvent which is a N-substituted propionic acid, and
• said coupler being a member selected from the group consisting of N-heptyl-1-hydroxy-2-naphthamide, N- (2-ethylhexyl)-1-hydroxy-2-naphthamide, l-phenyl-3- pentyl-S-pyrazolone, l-phenyl-3-nonyl-S-pyrazolone, and 2-butoxy-benzoylacetanilide
• said organic solvent being a member selected from the group consisting of Z-methyl-S-(N-n-octylacetamido)-propionic acid, 2-methyl-3- [N (2-ethylhexyl) butyramido] -pro pionic acid and 3-[N-(2-ethylhexyl)acetamido]propionic acid
• said color developing agent being a member selected from the group consisting of N,N- diethyl-p-phenylenediamine, 3-methyl-4-amino-N,
• a color diffusion transfer process which comprises:
• X represents a hydrogen atom or a methyl group
• R and R each represents an unsubstituted or substituted alkyl group, the sum of the number of carbon atoms in groups R and R being an integer from 7 to 11, said organic solvent being immiscible with water but miscible with an alkaline medium, and a N,N-dialkyl-p-phenylenediamine color developing agent, said coupler being insoluble in water, but soluble in an alkaline medium,
• said coupler is a member selected from the group consisting of N-heptyl-1- hydroxy-Z-naphthamide, N-(Z ethylhexyD-l-hydroxy-2- naphthamide, 1-phenyl-3-pentyl-5-pyrazolone, l-phenyl- 3-nonyl-5-pyrazolone, and 2'-butoxy-benzoylacetanilide.
• organic solvent is a member selected from the group consisting of 2- methyl-3-(N-n-octylacetamido)-propionic acid, Z-methyl- 3-[N-(Z-ethylhexyl)butyramido1-propionic acid, and 3- [N- (2-ethylhexyl) acetamido1-propionic acid.
• said color developing agent is a member selected from the group consisting of N,N-diethyl-p-phenylenecliamine, 3-methyl-4-amino- N,N-diethylaniline, and 3-methyl-4-amino-[N-ethyl-N-(Z- (methanesulfoamido)ethyl]-aniline.
• said alkaline medium is an aqueous solution of sodium hydroxide.
• said oxidizing agent incorporated in the image-receiving layer is a member selected from the group consisting of chloranil, acid clay and fog silver halide grains.
• a color diffusion transfer process which comprises:
• said coupler being a member selected from the group consisting of N-heptyl-l-hydroxy-Z-naphthamide, N-(2-ethylhexyl)-l-hydroxy-Z-naphthamide, l-phenyl-3-pentyl-5-pyrazolone, 1-phenyl-3-nonyl-5- pyrazolone, and 2'-butoxy-benzoylacetanilide
• said organic solvent being a member selected from the group consisting of 2-methyl-3-'(N-n-octylacetamido)- 13 14 propionic acid, 2-methyl-3-[N-(Z-ethylhexyl)butyr- 2,304,940 12/1942 Mannes et a1.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Family Applications (1)

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Cited By (6)

Families Citing this family (1)

• 1968
  • 1968-10-12 JP JP43074386A patent/JPS4832125B1/ja active Pending
• 1969
  • 1969-10-11 DE DE1951327A patent/DE1951327C3/de not_active Expired
  • 1969-10-13 GB GB50114/69A patent/GB1268240A/en not_active Expired
  • 1969-10-13 US US866022A patent/US3676124A/en not_active Expired - Lifetime

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