US3443951A - Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols - Google Patents

Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols Download PDF

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Publication number
US3443951A
US3443951A US468614A US3443951DA US3443951A US 3443951 A US3443951 A US 3443951A US 468614 A US468614 A US 468614A US 3443951D A US3443951D A US 3443951DA US 3443951 A US3443951 A US 3443951A
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Prior art keywords
phosphoric acid
sensitive
product
light
compounds
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US468614A
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English (en)
Inventor
Jozef Willems
Edwin Frans Hendricx
Robrecht Julius Thiers
Jozef Jan Onghena
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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

Definitions

  • 96-94 7 Claims ABSTRACT OF THE DISCLOSURE The formation of spots in radiation-sensitive silver halide material due to the presence of particles of heavy metals, compounds of heavy metals and the corrosion products of such metals or the compounds inhibited by the incorporation in the material of at least one watersoluble phosphoric acid ester of an aliphatic polyol, which per molecule contains at least two phosphoric acid groups from the class of the primary and secondary phosphoric acid groups.
  • the polyol is an aliphatic hydrocarbon polyol.
  • This invention relates to photographic light-sensitive silver halide materials containing compounds which prevent the formation of spots by the presence of particles of heavy metals and/or heavy metal compounds.
  • Said metal particles or particles of metal compounds are harmful particularly because they are chemically reactive, which means that they exert a secondary action upon the light-sensitive emulsion layer and aggravate the faults which are caused by the presence of said particles and which are mostly invisible by the unaided eye in such a way that according to the nature of the particle and the kind of the emulsion applied, light and dark spots become visible after treating the exposed lightsensitive material in the photographic baths.
  • the metal particles in the photographic layers can be affected and the corrosion products formed can diffuse away from the central nucleus. These corrosion products can exert a sensitizing or descnsitizing action on the emulsion so that after the normal bath-treatment the photographic material shows black and white spots respectively. Furthermore most of these metals or their compounds can act as reductors and cause a spontaneous development which leads to black spots. On the contrary, other influences such as affection of the latent image and hindrance of the development lead to white spots. In
  • the resulting spot is always larger than the dust particle which is the cause of this undesired phenomenon.
  • This can easily be checked, e.g., by bleaching out with a usual bleaching agent the silver from the material showing the black spot. Nearly always the black spot disappears but in the centre a very small nucleus remains which can only be seen by enlarging.
  • fine metal particles or dust consisting of metal compounds which are present in a nonlight-sensitive adjacent layer exert an equally disadvantageous influence on the upperor underlying light-sensitive layer.
  • the harmful corrosion products of the metal particles or the dissolved ingredients of the metal compounds indeed can reach by diffusion the light-sensitive layer to cause the above-mentioned faults.
  • Hitherto many compounds have already been proposed to prevent this formation of spots or at least to reduce such formation to a great extent. All these compounds, however, show one or more of the following disadvantages: an insufficient activity, an activity only in determined emulsions and in a well determined rather small pH range, and the occasioning of secondary effects on the silver halide emulsion layer such as desensitisation, fog formation and colouration.
  • the phosphoric acid derivatives proposed as spot inhibiting compounds show these disadvantages.
  • the phosphoric acid derivatives proposed hitherto are mainly alkali metaphosphates, alkali tripolyphosphates and alkali hexametaphosphates either or not mixed with alkali pyrophosphates.
  • the primary and secondary alkylor aryl-phosphates and acid alkylor aryl-pyrophosphates incorporated into the light-sensitive silver halide material do not even show any spotinhibiting action at all.
  • At least one Water-soluble phosphoric acid ester of an aliphatic polyol is present which contains per molecule at least two phosphoric acid groups from the class of the primary and secondary phosphoric acid groups.
  • These primary and secondary phosphoric acid groups can likewise be present in their salt form such as sodium, potassium or "ammonium salts or as amines.
  • phosphoric acid esters are active in all kinds of light-sensitive silver halide materials regardless of the pH and the sensitivity of the silver halide emulsion layer; moreover, they also appear to exert an antistatic and fog-depressing action on the light-sensitive material.
  • the phosphoric acid esters used according to the present invention can be prepared in different ways. It is necessary during this preparation to choose the mutual molar proportions of the reagents in such a way that always two or more primary or secondary phosphoric acid groups are introduced per molecule of aliphatic polyol. It can be determined in a simple way by potentiometric titration of the said functions present whether this has occurred.
  • a first method of preparation is the reaction of aliphatic polyols with phosphorus pentoxide.
  • mixtures of different compounds are formed which contain primary and/or secondary phosphoric acid groups.
  • polyphosphate structures are built as well.
  • Appropriate phosphoric acid esters can also be prepared by phosphorylation of aliphatic polyols with phosphorus oxychloride followed by hydrolysis of the acid chloride formed as an intermediate product.
  • A. J. Kirby (Chem. and Ind. 47 (1963), 1877), describes a process for the preparation of phosphoric acid esters which are appropriate for being applied according to the present invention, viz., a reaction of phosphorous acid and iodine with polyols.
  • Aliphatic polyols which are appropriate for the preparation of the said phosphoric acid esters are among others carbohydrates such as glucose, mannitol, sorbitol, glycerine, 1,4-butanediol, 1,2,4-butanetriol 1,2,6-hexanetriol, pentaerythritol, 2,4-dihydroxy-3-(hydroxymethyl)- pentane, 1,1,l-tris(hydroxymethy1)-propane and 4-hydroxy-2- (hydroxymethyl)-n-amy1 alcohol.
  • carbohydrates such as glucose, mannitol, sorbitol, glycerine, 1,4-butanediol, 1,2,4-butanetriol 1,2,6-hexanetriol, pentaerythritol, 2,4-dihydroxy-3-(hydroxymethyl)- pentane, 1,1,l-tris(hydroxymethy1)-propane and 4-hydroxy-2- (hydroxymethyl)-n-amy1 alcohol.
  • the compounds used according to the present invention can be present in difierent concentrations in the support, e.g., a paper support of the light-sensitive material and/ or in at least one of the water-permeable layers lying at the same side of the support as the light-sensitive silver halide emulsion layer. Said concentrations depend among others on the compound chosen and the nature of the layer wherein the compound is present.
  • the compounds according to the present invention are present in the light-sensitive silver halide emulsion layer itself and this in the most widely varying concentrations ranging from some mg. to and more g. per sq. m. of light-sensitive material. For the case the compounds are not present in the light-sensitive layer but in another layer, they are nevertheless active since they dilfuse into said light-sensitive layer.
  • the phosphoric acid esters according to the present invention usually are first dissolved, e.g., in water.
  • the support can then be soaked with such solution for the case that the compounds applied according to the present invention are incorporated into the support. If, however, the compounds are incorporated into a waterpermeable layer, in most cases their solution is added to the coating composition of the respective layer or layers.
  • the compounds used according to the present invention have the advantage that they do not impair at all the pursued photographic properties, such as, e.g., contrast, sensitivity and stability. Consequently, these compounds can be incorporated into high-sensitive as well as into low-sensitive emulsions, into high-contrast as well as into low-contrast emulsions, into acid as well as into alkaline emulsions.
  • a further advantage is that the compounds according to the invention do not impair at all the other products used in the manufacture of light-sensitive materials such as dispersing agents, colour couplers, surface-active agents, optical bleaching agents, antioxidising agents, sensitisers, fog-inhibiting agents, stabilisers, hardeners or plasticisers.
  • the compounds according to this invention can be used in all kinds of photographic negative and positive material, such as, e.g., printing material, X- ray film, graphic material, infrared-sensitive silver halide material and material for the application of the silver complex diffusion transfer process.
  • photographic negative and positive material such as, e.g., printing material, X- ray film, graphic material, infrared-sensitive silver halide material and material for the application of the silver complex diffusion transfer process.
  • photographic light-sensitive material not containing silver halide or in photographic nonlight-sensitive material the phosphoric acid esters described can successfully he used for avoiding spots caused by particles of heavy metal compounds.
  • the excess of (mono)ethyldihydrogen phosphate is removed by washing the reaction mass with anhydrous diethyl ether. The residue is placed under vacuum on a boiling water bath and thereafter cooled down to room temperature and dissolved in methanol. This solution is filtered over active carbon, and the methanol is distilled off under reduced pressure on a water 'bath at 40 to 50 C. Yield: 42.5 g.
  • the reaction product is a viscous oil which reacts as an acid.
  • PRODUCT 4.--REACTION PRODUCT OF GLUCOSE AND PHOSPHORUS PENTOXIDE A mixture of 50 g. (0.35 mol) of phosphorus pentoxide, g. (0.47 mol) of glucose and 500 cc. of diethyl ether is refluxed for 7 h. in a flask on a water bath, whilst thoroughly stirring. After standing overnight, the reaction product is sucked off. Yield: 138 g. The reaction product is hygroscopic and an aqueous solution thereof reacts as a strong acid.
  • PRODUCT 6.-PENTAERYTHRITOL TETRAKIS DI-HYDROGEN PHOSPHATE
  • T OH P-OCH: CHaOP
  • Example 1 A not yet quite dry adhesive layer applied to a cellulose triacetate support, is dusted with finely divided iron powder.
  • a strip A of this treated support is coated with a high-sensitive panchromatically sensitized silver bromide emulsion.
  • a strip B of this treated support is coated with the same silver bromide emulsion to which, however, per kg. of emulsion 1 g. of product 1 was added. After driving these two test strips are exposed in such a way that after developing for 9 min. at room temperature, fixing and rinsing, a density of 0.6 is obtained.
  • For development a solution of the following composition is used:
  • both strips A and B are rinsed for some seconds and then fixed for min. in a solution of the following composition:
  • the strips are then rised for 30 minutes in running water and finally dried.
  • the strips A shows numerous black spots whereas the strip B prepared according to the invention shows a uniform appearance and the same density all over its surface.
  • Example 2 Example 1 is repeated but instead of adding product 1 to the emulsion ready for coating, a same amount of product 3 is added thereto.
  • Example 3 A strip of crude paper A is coated with a barytalayer of the following composition:
  • the developed paper strip A displays numerous white spots each showing in the center the applied metal particle, whereas the strip B prepared according to the invention shows a uniform appearance and has the same density all over its surface.
  • Example 4 A strip of baryta-coated paper A is prepared as in Example 3.
  • a strip B is prepared in the same way with the same baryta composition to which, however, per kg. 5 g. of product 5 were added. Both baryta-coated strips are coated with a silver chlorobromide emulsion which on development gives a warm brown image tone. After developing, fixing and rinsing as in Example 3, numerous white spots are observed on the paper strip A, whereas the strip B prepared according to the invention shows a uniform appearance and possesses the same density all over its surface.
  • Example 5 A strip of crude photographic paper is coated with a baryta layer of the following composition:
  • Example 6 Example 5 is repeated but product 6 is replaced by 4 g. of product 1.
  • Example 7 Example 5 is repeated but product 6 is replaced by 4 g. of product 2.
  • Example 8 Example 5 is repeated but product 6 is replaced by 4 g. of product 3.
  • Example 9 Example 5 is repeated but product 6 is replaced by 4 g. of product 4.
  • Example 10 Example 5 is repeated but product 6 is replaced by 4 g. of product 5.
  • Photographic silver halide material sensitive to electromagnetic radiation comprising a support and a silver halide layer thereon, said material having incorporated therein at least one water-soluble phosphoric acid ester of an aliphatic polyol, which per molecule contains at least two phosphoric acid groups from the class of the primary and secondary phosphoric acid groups, said acid groups being in the form of the free acid or the water-soluble salts thereof.
  • Photographic light-sensitive silver halide material according to claim 1 wherein the water-soluble phosphoric acid ester is present in the light-sensitive silver halide emulsion layer.
  • the material of claim 1 including at least one waterpermeable layer in water-permeable relationship with said halide layer on the same side of the support as said halide layer, said phosphoric acid ester being present in said water-permeable layer.
  • the method of inhibiting the formation in silver halide material sensitive to electromagnetic radiation of spots caused by the presence of particles of heavy metals, compounds of heavy metals and the corrosion products thereof which comprises the step of incorporating in said material at least one water-soluble phosphoric acid ester of an aliphatic polyol, which per molecule contains at least two phosphoric acid groups from the class of the primary and secondary phosphoric acid groups, said acid groups being in the form of the free acid or the water-soluble salts thereof.

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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)
US468614A 1964-07-02 1965-06-30 Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols Expired - Lifetime US3443951A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4324856A (en) * 1979-10-11 1982-04-13 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
US4340665A (en) * 1981-03-04 1982-07-20 E. I. Du Pont De Nemours And Company Silver halide film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3169863A (en) * 1962-07-21 1965-02-16 Agfa Ag Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions
US3258338A (en) * 1960-12-29 1966-06-28 Claeys Daniel Alois Photographic material containing softening agent
US3332777A (en) * 1963-01-04 1967-07-25 Ciba Ltd Silver halide emulsion preparation using phosphoric acid esters as flocculants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3258338A (en) * 1960-12-29 1966-06-28 Claeys Daniel Alois Photographic material containing softening agent
US3169863A (en) * 1962-07-21 1965-02-16 Agfa Ag Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions
US3332777A (en) * 1963-01-04 1967-07-25 Ciba Ltd Silver halide emulsion preparation using phosphoric acid esters as flocculants

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4324856A (en) * 1979-10-11 1982-04-13 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
US4340665A (en) * 1981-03-04 1982-07-20 E. I. Du Pont De Nemours And Company Silver halide film
EP0059479A3 (en) * 1981-03-04 1982-11-10 E.I. Du Pont De Nemours And Company Improved silver halide film

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NL6508534A (en)) 1965-12-27

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