US3185569A - Photographic silver halide material containing lactose - Google Patents

Photographic silver halide material containing lactose Download PDF

Info

Publication number
US3185569A
US3185569A US266040A US26604063A US3185569A US 3185569 A US3185569 A US 3185569A US 266040 A US266040 A US 266040A US 26604063 A US26604063 A US 26604063A US 3185569 A US3185569 A US 3185569A
Authority
US
United States
Prior art keywords
silver halide
lactose
silver
emulsions
gelatin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US266040A
Inventor
Weber Hans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Application granted granted Critical
Publication of US3185569A publication Critical patent/US3185569A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances

Definitions

  • the covering power of photosensitive photographic silverhalide preparations can be increased by adding lactose to the photosensitive layer and/or to the auxiliary layers, e.g., sublayers, filter layers and anti-abrasion layers, with no occurrence of the drawbacks mentioned above. Addition of lactose then not only enhances covering power, but also substantially diminishes fogging. These results are wholly unexpected and were in no way predictable. As is known in the art, lactose is not even a macromolecular compound, but has a comparatively low molecular weight and is also characterized by substantial solubility in water. Hence, from this it would be expected that the lactose would be leached out of the film layers during processing so that its effect would be lost.
  • lactose is not even a macromolecular compound, but has a comparatively low molecular weight and is also characterized by substantial solubility in water. Hence, from this it would be expected that the lactose would be leached out of the film layers during processing so
  • the present invention offers the possibility of employing a low-molecular substance for the specified purpose, with the advantage that it does not affect the viscosity of the emulsion.
  • reducing agents to photosensitive emulsions 3,185,569 Patented May 25, 1965
  • Preparation of the emulsions according. to this invention may be carried out by the usual methods.
  • the lactose is added to the emulsion in amounts of 5 55 g. per liter, the addition being advantageously effected either before finishing the emulsion or immediately before coating the film. Addition may, however, be effected at any other time as maybe desired during the emulsification process.
  • lactose to the photosensitive layer and/ or to the auxiliary layers in amounts of 5-55 g. to 20-100 g. of silver bromide.
  • the gelatino-silver halide emulsions of the invention contain at least 20% by weight of lactose based on silver halide. On a dry basis, the lactose-containing gelatinosilver halide emulsions contain 35% to 70% silver halide, 20% to 60% gelatin, and 5% to 40% lactose, all by weight.
  • the process is applicable to all silver halide: gelatin emulsions but is particularly effective in coarse-grained high-sensitivity emulsions.
  • the lactose can be added to gelatin silver chloride, silver bromide, silver iodobromide, silver chlorobromide and other simple and mixed silver halide emulsions.
  • the final emulsions can contain any of the wellknown optical sensitizing dyes as well as non-optical sensitizers such as sulphur sensitizers, e.g., allyl isothiocyanate, allyl diethyl thiourea, phenyl isothiocyanate and sodium thiosulfate; the polyoxyalkylene ethers disclosed in Blake et al., U.S.
  • Other non-optical sensitizers such as amines as taught by Staud et al., U.S. Patent 1,925,508 and metal salts as taught by Baldsiefen, U.S. Patent 2,540,085 and Baldsiefen et al., U.S. Patent 2,540,086 may also be used.
  • Antifoggants e.g., benzotriazole and triazaindenes can be used as well as the usual hardeners, i.e., chrome alum, formaldehyde, etc.
  • the modified lactose-containing gelatino-silver halide emulsions may be coated on any suitable support such as paper or films composed of cellulosic esters, e.g., cellulose triacetate, cellulose acetate/butyrate; superpolymers, e.g., polyvinyl chloride co vinyl acetate, polyvinyl acetals, e.g., formal and acetal; polystyrene, polyamides, e.g., polyhexamethylene adipamide, and polyesters, e.g., polyethylene terephthalate, polyethylene terephthalate/ isophthalate and those polyesters obtainable by condensing terephthalic acid or dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane-1,4-dimethanol (hexahydro-p-xylene alcohol).
  • lactose may be used in emulsions according to this invention. Because of its low price, it has substantial commercial superiority over the dextrans.
  • Lactose 40 g. per kg. of emulsion ready for coating, is added to emulsion B while no lactose is added to emulsion A.
  • the emulsions are cast on a film base, yielding films A and B.
  • a Wedge pattern was copied on each of these films. They were developed in a developer having the composition:
  • a photographic gelatin-silver halide emulsion layer containing on a dry basis to 70% silver halide, 20% to 60% gelatin and 5% to lactose, all by weight.
  • a photographic element comprising a gelatino-silver halide emulsion layer having in intimate association therewith 5 to 22 grams of lactose per 20 to 100 grams of silver halide.
  • a photographic element comprising a gelatino-sil- -ver halide emulsion layer having in intimate association therewith on a dry basis 35% to 70% silver halide, 20% to gelatin, and 5% to 40% lactose, by weight.

Description

United States Patent This invention relates to a novel and particularly advantageous photosensitive photographic silver halide material having improved properties.
It is desirable for many reasons to attain the blackening of photosensitive photographic silver halide preparations, essential to image formation, with the smallest possible application of silver, halide. Films with slight application of silver and gelatin have, in addition to the considerable economic advantage, also the great merit that they can be processed and dried in a very short time, which is of utmost significance'in view of the steady increase in automatic processing. 9 In this connection, it is known in the art that the covering power of gelatin-containing photographic emulsions can be increased by replacing a portion of the gelatin with macromolecular compounds, for example, N-vinyl lactame polymers, dextrin, dextran or the like. These substances also have the effect that for the same quantity of applied silver halide the developed image is given a substantial increment in maximum density and in contrast.
But substances used in the prior art for increasing covering power have serious drawbacks. Since the prior art concerned itself with macromolecular substances,
which must be added to the gelatin in comparatively large amounts, there is an unfavorable'and uncontrollable effect on the viscosity of the emulsions. Moreover, these substances frequently display low compatibility with the photosensitive emulsion, so that they can be used only in combination with special stabilizers.
Now it has been found that the covering power of photosensitive photographic silverhalide preparations can be increased by adding lactose to the photosensitive layer and/or to the auxiliary layers, e.g., sublayers, filter layers and anti-abrasion layers, with no occurrence of the drawbacks mentioned above. Addition of lactose then not only enhances covering power, but also substantially diminishes fogging. These results are wholly unexpected and were in no way predictable. As is known in the art, lactose is not even a macromolecular compound, but has a comparatively low molecular weight and is also characterized by substantial solubility in water. Hence, from this it would be expected that the lactose would be leached out of the film layers during processing so that its effect would be lost. Surprisingly, however, this does not occur; instead, the effect of lactose in giving greater covering power is fully retained even in the final processed film. Thus, the present invention offers the possibility of employing a low-molecular substance for the specified purpose, with the advantage that it does not affect the viscosity of the emulsion.
Again, it is known to those skilled in the art that addition of reducing agents to photosensitive emulsions 3,185,569 Patented May 25, 1965 Preparation of the emulsions according. to this invention may be carried out by the usual methods. Preferably the lactose is added to the emulsion in amounts of 5 55 g. per liter, the addition being advantageously effected either before finishing the emulsion or immediately before coating the film. Addition may, however, be effected at any other time as maybe desired during the emulsification process.
Along the same line, it is especially advantageous to add the lactose to the photosensitive layer and/ or to the auxiliary layers in amounts of 5-55 g. to 20-100 g. of silver bromide.
The gelatino-silver halide emulsions of the invention contain at least 20% by weight of lactose based on silver halide. On a dry basis, the lactose-containing gelatinosilver halide emulsions contain 35% to 70% silver halide, 20% to 60% gelatin, and 5% to 40% lactose, all by weight.
' The process is applicable to all silver halide: gelatin emulsions but is particularly effective in coarse-grained high-sensitivity emulsions.
The lactose can be added to gelatin silver chloride, silver bromide, silver iodobromide, silver chlorobromide and other simple and mixed silver halide emulsions. The final emulsions, moreover, can contain any of the wellknown optical sensitizing dyes as well as non-optical sensitizers such as sulphur sensitizers, e.g., allyl isothiocyanate, allyl diethyl thiourea, phenyl isothiocyanate and sodium thiosulfate; the polyoxyalkylene ethers disclosed in Blake et al., U.S. Patent 2,400,532 and the polyglycols disclosed in Blake et al., U.S. Patent 2,423,549. Other non-optical sensitizers such as amines as taught by Staud et al., U.S. Patent 1,925,508 and metal salts as taught by Baldsiefen, U.S. Patent 2,540,085 and Baldsiefen et al., U.S. Patent 2,540,086 may also be used. Antifoggants, e.g., benzotriazole and triazaindenes can be used as well as the usual hardeners, i.e., chrome alum, formaldehyde, etc.
The modified lactose-containing gelatino-silver halide emulsions may be coated on any suitable support such as paper or films composed of cellulosic esters, e.g., cellulose triacetate, cellulose acetate/butyrate; superpolymers, e.g., polyvinyl chloride co vinyl acetate, polyvinyl acetals, e.g., formal and acetal; polystyrene, polyamides, e.g., polyhexamethylene adipamide, and polyesters, e.g., polyethylene terephthalate, polyethylene terephthalate/ isophthalate and those polyesters obtainable by condensing terephthalic acid or dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane-1,4-dimethanol (hexahydro-p-xylene alcohol). The vinylidene chloride copolymer-coated oriented polyester films of Alles et al., U.S. Patent 2,- 627,088 and Alles, U.S. Patent 2,779,684 are especially suitable.
Commercially available lactose may be used in emulsions according to this invention. Because of its low price, it has substantial commercial superiority over the dextrans.
Example A high-sensitivity gelatimsilver iodobromide emulsion, containing 7.5% gelatin and 8.25% silver halide, is treated with the needed emulsion additives or adjuvants, after the finishing process, and is divided into 2 parts (A) and (B).
Lactose, 40 g. per kg. of emulsion ready for coating, is added to emulsion B while no lactose is added to emulsion A.
The emulsions are cast on a film base, yielding films A and B.
1 Consisting of approx. 98% silver bromide and approx. 2% silver iodide.
A Wedge pattern was copied on each of these films. They were developed in a developer having the composition:
Development: 3 minutes at 20 C.; fixing: about 5 minutes.
After washing and drying the film strips, measurements were made of maximum density at like application of silver, and of fogging:
Maximum density I Fogging 2. 7 Film B 3. 5 01 Film A "I I 07 An important advantage of the invention is that it provides a simple and economical way of providing photographic gelatin-silver halide emulsions of increased covering power.
Still other advantages will be apparent from the above description to those skilled in the art.
I claim:
1. A photographic gelatin-silver halide emulsion containing at least 20%, by weight, of lactose, by weight of silver halide.
2. A photographic gelatin-silver halide emulsion layer containing on a dry basis to 70% silver halide, 20% to 60% gelatin and 5% to lactose, all by weight.
3. A photographic element comprising a gelatino-silver halide emulsion layer having in intimate association therewith 5 to 22 grams of lactose per 20 to 100 grams of silver halide.
4. An element according to claim 3 wherein the lactose is in the emulsion layer.
5. An element according to claim 3 wherein the silver halide is silver iodobromide.
6. A photographic element comprising a gelatino-sil- -ver halide emulsion layer having in intimate association therewith on a dry basis 35% to 70% silver halide, 20% to gelatin, and 5% to 40% lactose, by weight.
7. An element according to claim 6 wherein the lactose is in the emulsion layer.
8. An element according to claim 6 wherein the silver halide is silver iodobromide.
References Cited by the Examiner Ser. No. 318,113, Diamant-Eerde (A.P.C.), published May 4, 1943, abandoned.
Wood: Journal Photographic Science, vol. 6, pages 91-66 (1958).
Friedman: Journal American Chemical Society, vol. 52, pages 1305-10 (1930).
Basinski et al.: Chemical Abstracts, vol. 6, page 13627 (1957).
NORMAN G. TORCHIN, Primary Examiner.

Claims (1)

1. A PHOTOGRAPHIC GELATIN-SILVER HALIDE EMULSION CONTAINING AT LEAST 20%, BY WEIGHT, OF LACTOSE, BY WEIGHT OF SILVER HALIDE.
US266040A 1962-08-29 1963-03-18 Photographic silver halide material containing lactose Expired - Lifetime US3185569A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA41045A DE1153990B (en) 1962-08-29 1962-08-29 Halogen silver photographic light sensitive material

Publications (1)

Publication Number Publication Date
US3185569A true US3185569A (en) 1965-05-25

Family

ID=6932294

Family Applications (1)

Application Number Title Priority Date Filing Date
US266040A Expired - Lifetime US3185569A (en) 1962-08-29 1963-03-18 Photographic silver halide material containing lactose

Country Status (4)

Country Link
US (1) US3185569A (en)
BE (1) BE636720A (en)
DE (1) DE1153990B (en)
GB (1) GB978880A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607346A (en) * 1969-04-21 1971-09-21 Eastman Kodak Co Layers method of wet transferring unexposed photographic emulsion
US3936300A (en) * 1972-11-02 1976-02-03 Polaroid Corporation Glucoside humectant as silver halide emulsion stabilizer
US5232827A (en) * 1991-09-09 1993-08-03 Eastman Kodak Company Stabilized photographic recording materials
US5370986A (en) * 1990-03-05 1994-12-06 Eastman Kodak Company Stabilization of photographic recording materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607346A (en) * 1969-04-21 1971-09-21 Eastman Kodak Co Layers method of wet transferring unexposed photographic emulsion
US3936300A (en) * 1972-11-02 1976-02-03 Polaroid Corporation Glucoside humectant as silver halide emulsion stabilizer
US5370986A (en) * 1990-03-05 1994-12-06 Eastman Kodak Company Stabilization of photographic recording materials
US5232827A (en) * 1991-09-09 1993-08-03 Eastman Kodak Company Stabilized photographic recording materials

Also Published As

Publication number Publication date
BE636720A (en)
DE1153990B (en) 1963-09-05
GB978880A (en) 1964-12-23

Similar Documents

Publication Publication Date Title
US3220839A (en) Photographic emulsions containing isothiourea derivatives
US3063838A (en) Photographic emulsions and elements containing dextran
US3287135A (en) Antifoggants for silver halide emulsions on a linear polyester support
US3232764A (en) Gelatin compositions adapted for the preparation of hardened coatings
US3499761A (en) Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents
US3519426A (en) Preparation of silver halide emulsions having high covering power
US3582346A (en) Photographic silver halide emulsion stabilized with ethylene-diurea
US3185569A (en) Photographic silver halide material containing lactose
US3361564A (en) Amine borane as fogging agent in direct positive
US3488709A (en) Stabilizing silver halide emulsions with cadmium bromide
US3565625A (en) Photographic elements having thiazolidine compounds in light-in-sensitive layers
US3255013A (en) Increasing the sensitivity of photographic emulsions
US4126472A (en) Process of making a lithographic photosensitive silver halide emulsion having reduced susceptibility to pressure containing an iridium compound, a hydroxytetrazaindene and a polyoxyethylene
US3272631A (en) Haze reduction of photographic emulsions containing a covering power agent
US2995444A (en) Stabilization of photographic emulsions sensitized with alkylene oxide polymers
US3671258A (en) Speed increasing combination of stabilizers for radiographic elements
US3085009A (en) Photographic emulsions and elements containing a water soluble mannan
US3345175A (en) High edge-gradient photosensitive material
US3069267A (en) Photographic emulsions containing hydrolyzed glycogen
US3671255A (en) Silver halide emulsion fog inhibited with quaternary ammonium,triazole and tetrazaindene compounds
US3085010A (en) Photographic emulsions and elements containing a water soluble laminarin
US3006762A (en) Sensitizers for photographic emulsions
US3597213A (en) Fog reduction in photographic silver halide emulsions
US3137575A (en) Photographic silver halide emulsions and elements containing a polyfructose
US3615490A (en) Photographic overcoat comprising a benzotriazole toning agent and a silver salt of 5-mercapto-1-substituted tetrazole