EP0049449B1 - Lichtempfindliches fotografisches Silberhalogenid-Aufzeichnungsmaterial - Google Patents

Lichtempfindliches fotografisches Silberhalogenid-Aufzeichnungsmaterial Download PDF

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Publication number
EP0049449B1
EP0049449B1 EP81107680A EP81107680A EP0049449B1 EP 0049449 B1 EP0049449 B1 EP 0049449B1 EP 81107680 A EP81107680 A EP 81107680A EP 81107680 A EP81107680 A EP 81107680A EP 0049449 B1 EP0049449 B1 EP 0049449B1
Authority
EP
European Patent Office
Prior art keywords
diones
compounds
alkyl
oder
ring
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
Application number
EP81107680A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0049449A1 (de
Inventor
Hans Dr. Langen
Erich Dr. Wolff
Erwin Dr. Ranz
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.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
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 Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0049449A1 publication Critical patent/EP0049449A1/de
Application granted granted Critical
Publication of EP0049449B1 publication Critical patent/EP0049449B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/33—Spot-preventing agents
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • the invention relates to a photographic silver halide recording material which, in addition to a crosslinking agent which activates the carboxyl groups of the gelatin used as binders, contains a compound which is capable of reacting as an aldehyde scavenger.
  • Photographic recording materials usually consist of a layer support and light-sensitive gelatin-containing silver halide emulsion layers and / or non-light-sensitive auxiliary layers, likewise containing gelatin, applied thereon.
  • the light-sensitive silver halide gelatin emulsion layers of color photographic recording materials contain the color components required to form the image dyes in the three primary colors.
  • the multi-layered recording materials mentioned here in black and white and color photography and their production are generally known and are described, for example, in the "Photography” chapter in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18.
  • crosslinking agents which are also called hardening agents.
  • crosslinking agents which are also called hardening agents.
  • inorganic and organic, photographically inert compounds which can crosslink the gelatin via the carboxyl groups or the amino groups are suitable as hardening agents.
  • curing agents are aldehydes, e.g. B. formaldehyde, glyoxal, glutaraldehyde, aldehyde acids, e.g. B. mucochloric acid, diketones, e.g. B. diacetyl, dihalides, e.g.
  • aldehydes such as formaldehyde, glyoxal, glutaraldehyde or succinaldehyde as curing agents are associated with certain difficulties.
  • aldehydes can not only cause crosslinking of the gelatin layers that is difficult to limit, they can also impair the functionality of the color components contained in the layers, and they can give rise to the formation of fog.
  • This disadvantageous effect is also to be expected if the aldehydes have not been specifically incorporated into the photographic materials, but, e.g. B. during an unintended storage of the photographic material in an aldehyde-containing atmosphere in the photographic layers.
  • aldehyde scavengers In order to avoid the disadvantages caused by aldehydes described, attempts have been made to incorporate so-called aldehyde scavengers into the photographic materials, which are compounds which are able to trap the aldehyde.
  • DE-A-1772816 to add photographic layers, for example N, N'-ethylene urea, 2,3-dihydroxynaphthalene or dimedone, in order to fix formaldehyde.
  • DE-A-2332426 describes a photographic recording material which, in addition to a vinylsulfonyl hardener, contains an acyclic urea as aldehyde remover in one of its colloid layers.
  • US-A-3 652 278 relates to a method for reducing fog in photographic materials to be stored in an atmosphere containing formaldehyde.
  • a compound from the group N, N'-ethylene urea, 2,3-dihydroxynaphthalene and 1,1-dimethyl-3,5-diketocyclohexane is then incorporated into the silver halide emulsion of the material.
  • US-A-2309492 It is further known from US-A-2309492 to process photographic materials which contain an aldehyde hardener in the presence of an organic compound which is able to react with the aldehyde.
  • the compounds include hydroxylamines, hydrazines, hydrazo compounds, semicarbazides, naphthalenediamines and dimethyldihydroresorcinol.
  • US-A-3 168400 also relates to a method for stabilizing photographic images. The method is to harden the binder of the photographic material before developing the material and after exposure to an aldehyde, and then removing the unused aldehyde by treatment with the aqueous solution of an amine compound. Suitable amines are e.g. B.
  • Aldehyde-containing photographic materials are treated according to DE-A-2227 144 in baths containing hydroxylamine or a water-soluble salt of Hydroxylamine and an aromatic polyhydroxyl compound with 2 hydroxyl groups in the ortho position, e.g. B. contains an o-dihydroxy compound from the benzene series.
  • the invention has for its object to develop a photographic recording material which is protected against fogging, especially in the case of prolonged storage under the action of aldehydes, and whose contrast and sensitivity are not adversely affected by such storage.
  • color photographic recording materials the gelatin layers of which are hardened with a hardening agent from the group consisting of the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium salts, and which also contain a diketo compound of the formula given, are largely immune to the harmful effects caused by aldehydes .
  • a hardening agent from the group consisting of the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium salts, and which also contain a diketo compound of the formula given.
  • the following compounds may be mentioned as examples of hardening agents which can advantageously be used according to the invention: Syrup, very hygroscopic Syrup, very hygroscopic Mp 112 ° C Mp 103 ° C Mp 87-89 ° C Mp 108-110 ° C Syrup, hygroscopic Mp 105-107 ° C syrup Mp 103-105 ° C Mp 75-77 ° C Mp 110-112 ° C Mp 95-96 ° C Mp 106 ° C Molecular weight over 1000 Mp 66-68 ° C Syrup, hygroscopic M.p.
  • the cyclic diketo compounds of the invention can be used in the layers of photographic recording materials together with the curing agents mentioned, without the two additives adversely affecting one another in any way.
  • the diketo compounds can be added to the casting solution of one or more of the sub-layers of the photographic recording material, depending on the conditions of the casting. In general, it is sufficient to coat the recording material with a top layer which contains the diketo compound. The layered structure is then adequately protected against the penetration of aldehyde vapors.
  • the use of the diketo compounds in this form has proven particularly useful for color photographic multilayer materials.
  • the amount of the diketo compound applied with the top layer can be dimensioned such that the compound diffusing into the layer structure during the drying process is evenly distributed over the layers of the structure containing color components, thereby providing an optimal protective effect is achieved.
  • the diketo compounds can be introduced in all water-miscible solvents or in water itself. Particularly advantageous are low-boiling solvents, which can be easily removed when the photographic material is poured on, e.g. B. methanol, ethanol, propanol, (t) -butanol, acetone, methyl ethyl ketone, acetonitrile.
  • cyclic diketo compounds to be used are understandably dependent on the extent to which protection of the recording material is required. They will therefore depend on the aldehyde concentration to be considered, the sensitivity of the components within the photographic material to be protected and finally the solubility of the cyclic diketo compounds used.
  • aldehydes present in the atmosphere for which aldehydes present in the atmosphere are responsible, generally at least 0.05 mol of the cyclic diketo compound per mol of hardener is sufficient.
  • the use of 0.1 to 6 moles of diketo compound per mole of curing agent is preferred, with amounts of 0.2 to 2 moles of diketo compound per mole of curing agent having proven particularly suitable.
  • hydrophilic colloids in the layers of the recording material in addition to the gelatin, colloidal albumin, agar, gum arabic, dextrans, alginic acid, cellulose derivatives, e.g. B. up to an acetyl content of 19 to 26% hydrolyzed cellulose acetate, polyacrylamides, imidated polyacrylamides, cein, vinyl alcohol polymers with urethane / carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol, vinyl cyanoacetate mixed polymers, polyvinyl alcohols, polyvinylpyrrolidones, such as hydrolyzed polymers, vinyl hydrolyzed polymers the polymerization of proteins and saturated acylated proteins with monomers obtained with vinyl groups, polyvinylamines, polyaminoethyl methacrylates and polyethyleneimines can be used.
  • carbamoylpyridinium Cyclic diketo compounds used with carbamoyloxypyridinium hardeners have proven to be particularly advantageous in that they do not in any way impair the sensitometric properties of the photographic material, although in principle they would be capable of coupling due to the presence of an active carbon atom.
  • carbamoylpyridinium Cyclic diketo compounds used with carbamoyloxypyridinium hardeners have proven to be particularly advantageous in that they do not in any way impair the sensitometric properties of the photographic material, although in principle they would be capable of coupling due to the presence of an active carbon atom.
  • aldehyde scavengers unlike the compounds known as aldehyde scavengers, they have a high reactivity towards aldehydes, which makes the use of the curing agent mentioned possible in practice.
  • the samples were in a size of 35 x 250 mm for 7 days at room temperature in a vessel with a volume of 27 l in which there was a mixture of 650 g glycerol, 350 g water and 1 ml 30% formaldehyde found, stored and then checked in comparison with a normally stored material.
  • the purple residual color density remaining in% of the color density 1.5 via veil was evaluated in each case.
  • the effect of the present 1,3-diketo compounds is compared with that of known aldehyde removers.
  • the diketo compounds and the comparison compounds 170 mg each of layer 7 of example 1, 180 mg of layer 8 of example 1 and 100 mg of layer 9 of example 1 were added.
  • Compound 11/15 was used as the curing agent.
  • Table 2 shows that practically only the cyclic 1,3-diketo compounds of the invention have a protective effect.
  • diketo compound no. 26 Of the diketo compound no. 26, 220 g are added to layers 1 and 2 from example 1 and 145 mg to layers 7, 8 and 9 of example 1. Compound No. 11/10 is used as the hardening agent in all cases. A purple color density of 90% was measured on all 5 samples after storage under a formalin atmosphere. As the example shows, the same protective effects are achieved, regardless of whether the diketo compound is embedded in a layer which lies above or below the purple layer to be protected or which is the purple layer itself.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Pyridine Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
EP81107680A 1980-10-08 1981-09-28 Lichtempfindliches fotografisches Silberhalogenid-Aufzeichnungsmaterial Expired EP0049449B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3037912 1980-10-08
DE19803037912 DE3037912A1 (de) 1980-10-08 1980-10-08 Lichtempfindliches fotografisches silberhalogenid-aufzeichnungsmaterial

Publications (2)

Publication Number Publication Date
EP0049449A1 EP0049449A1 (de) 1982-04-14
EP0049449B1 true EP0049449B1 (de) 1983-09-28

Family

ID=6113849

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81107680A Expired EP0049449B1 (de) 1980-10-08 1981-09-28 Lichtempfindliches fotografisches Silberhalogenid-Aufzeichnungsmaterial

Country Status (5)

Country Link
US (1) US4418142A (enrdf_load_stackoverflow)
EP (1) EP0049449B1 (enrdf_load_stackoverflow)
JP (1) JPS57100423A (enrdf_load_stackoverflow)
CA (1) CA1164709A (enrdf_load_stackoverflow)
DE (2) DE3037912A1 (enrdf_load_stackoverflow)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60237445A (ja) * 1984-05-10 1985-11-26 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS60258545A (ja) * 1984-05-10 1985-12-20 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS6153272A (ja) * 1984-08-24 1986-03-17 Shionogi & Co Ltd グルタル酸誘導体の製法
US4639415A (en) * 1984-09-17 1987-01-27 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material containing a magenta color image-forming coupler
DE3624301A1 (de) * 1986-05-28 1987-12-10 Miles Lab Gehaertete reagenzschichten und verfahren zu deren herstellung
JP2565766B2 (ja) * 1988-02-09 1996-12-18 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0431371U (enrdf_load_stackoverflow) * 1990-07-11 1992-03-13
DE69535305T2 (de) * 1994-09-09 2007-06-21 Koyama, Shozo, Matsumoto Mittel zum herabsetzen von molekülfunktionen
WO2018145283A1 (en) 2017-02-09 2018-08-16 Dow Global Technologies Llc Polyurethane foams having low levels of aldehyde emissions
JP7232317B2 (ja) 2018-08-02 2023-03-02 ダウ グローバル テクノロジーズ エルエルシー ポリウレタン発泡体のアルデヒド排出量を減少させるための方法
KR102649156B1 (ko) 2018-08-02 2024-03-20 다우 글로벌 테크놀로지스 엘엘씨 폴리우레탄 폼에서 알데히드 방출을 감소시키는 방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447926A (en) * 1965-01-22 1969-06-03 Eastman Kodak Co Color photographic silver halide elements containing 4-substituted urazoles and/or cycloalkane-1,3-diones
US3652278A (en) * 1967-07-08 1972-03-28 Fuji Photo Film Co Ltd Pre-development process for reducing fog in silver halide photographic materials
US3811891A (en) * 1972-06-27 1974-05-21 Eastman Kodak Co Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger
DE2439551C2 (de) * 1974-08-17 1985-11-21 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur Härtung photographischer Schichten

Also Published As

Publication number Publication date
JPS57100423A (en) 1982-06-22
US4418142A (en) 1983-11-29
JPH0226211B2 (enrdf_load_stackoverflow) 1990-06-08
CA1164709A (en) 1984-04-03
EP0049449A1 (de) 1982-04-14
DE3161041D1 (en) 1983-11-03
DE3037912A1 (de) 1982-05-27

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