EP0411819A2 - Elément photographique à l'halogénure d'argent travaillant en négatif manipulable À la lumière du jour - Google Patents
Elément photographique à l'halogénure d'argent travaillant en négatif manipulable À la lumière du jour Download PDFInfo
- Publication number
- EP0411819A2 EP0411819A2 EP90308153A EP90308153A EP0411819A2 EP 0411819 A2 EP0411819 A2 EP 0411819A2 EP 90308153 A EP90308153 A EP 90308153A EP 90308153 A EP90308153 A EP 90308153A EP 0411819 A2 EP0411819 A2 EP 0411819A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- halide photographic
- photographic element
- water
- layer
- 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.)
- Ceased
Links
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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
-
- 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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
Definitions
- the present invention relates to UV sensitive negative acting silver halide photographic elements, and more particularly to UV sensitive negative acting silver halide photographic elements which can be handled under room lighting conditions without significant loss in image density, and which upon development of a half-tone image thereon can be dry etched with improved performance characteristics.
- Light sensitive recording materials may suffer from a phenomenon known as halation which causes degradation in the quality of the recorded image. Such degradation may occur when a fraction of the imaging light which strikes the photosensitive layer is not absorbed but passes through to the film base on which the photosensitive layer is coated. A portion of the light reaching the base may be reflected back to strike the photosensitive layer from the underside. Light thus reflected may, in some cases, contribute significantly to the total exposure of the photosensitive layer. Any particulate matter in the photosensitive element may cause light passing through the element to be scattered. Scattered light which is reflected from the film base will, on its second passage through the photosensitive layer, cause exposure over an area adjacent to the point of intended exposure. It is this effect which leads to image degradation.
- halation causes degradation in the quality of the recorded image. Such degradation may occur when a fraction of the imaging light which strikes the photosensitive layer is not absorbed but passes through to the film base on which the photosensitive layer is coated. A portion of the light reaching the base may be reflected back to strike the photosensitive layer from the underside
- Silver halide based photograhic materials are prone to this form of image degradation since the photosensitive layers contain light scattering particles.
- the effect of light scatter on image quality is well documented and is described, for example, in T. H. James "The Theory of the Photographic Process", 4th Edition, Chapter 20, Macmillan 1977.
- a similar effect may be achieved by a light absorbing layer interposed between the photosensitive layer and the base.
- This construction described as an "antihalation underlayer” is applicable to photosensitive coatings on transparent or non-transparent bases.
- a light absorbing substance may be incorporated into the photosensitive layer itself, in order to absorb scattered light. Substances used for this purpose are known as "acutance dyes". It is also possible to improve image quality by coating a light absorbing layer above the photosensitive layer of a wet processed photographic element. Coatings of this kind, described in U.S. Patent Specification No. 4,312,941 prevent multiple reflections of scattered light between the internal surfaces of a photographic element.
- Antihalation dyes can be rendered colorless by way of heat bleaching, development solution bleaching, a specific bleaching solution, or removal from the medium in a dissolving bath.
- the wavelength of sensitivity of the medium and hence the wavelength of absorption of the antihalation dye, is outside the visible region, it is not necessary to decolorize the antihalation dye since it has no color (i.e., it is not visible).
- Some antihalation dyes may have absorption tails that extend into the visible region and would therefore have to be decolorized (e.g., U.S. Patent 4,581,325).
- U.S. Reissue Patent No. 30,303 describes UV absorbing dyes useful as filter dyes in photographic elements.
- the claims are for molecules of the type wherein n is 1 or 2, when n is 1, R1 and R2 are independently chosen to represent hydrogen, an alkyl group of 1 to 10 carbon atoms, or a cyclic alkyl group of 5 or 6 carbon atoms provided that R1 and R2 cannot both be hydrogen, or R1 and R2 taken together represent the atoms necessary to complete a cyclic amino group and when n is 2 at least one of R1 and R2 is alkylene and G represents an electron withdrawing group.
- the first patent refers to polymeric versions of the dye class and is fairly far removed from our proposed use.
- Advantages are claimed for improved absorption profiles, easier and more consistent dispersions obtainable and show a reduced speed loss compared to the derivatives claimed in Reissue Patent 30,303.
- the main application is for the UV filter dye in the color negative constructions.
- the dyes are hydrophobic in U.S. Patents 4,307,184 and 4,576,908 and presumably would not be bleached in processing.
- a UV sensitive negative acting silver halide photographic element for contacting processes which can be safely handled under white light, said element comprising a support, a hydrophilic colloidal silver halide emulsion layer comprising negative acting silver halide grains, and a backside coated antihalation layer, wherein said backside coated antihalation layer comprises a water removable UV absorbing compound having at least 80% absorption in the range of 350 to 400 nm.
- the present invention relates to a UV sensitive negative acting silver halide photographic element comprising a support, a hydrophilic colloidal silver halide emulsion layer comprising negative acting UV sensitive photographic silver halide grains, and at least a backside coated UV absorbing antihalation layer, wherein said antihalation layer comprises a water removable UV absorbing compound having at least 80% of absorption in the range of 350 to 400 nm.
- the UV absorbing compounds for use in the silver halide photographic element according to the present invention correspond to the general formula: in which: R1 and R2, the same or different, each represents an alkyl group, an aryl group or a cyclic alkyl group, or R1 and R2 taken together represent the atoms necessary to complete a cyclic amino group, G represents an electron withdrawing group, and at least one of R1, R2 and G is substituted with a water solubilizing group.
- R1 and R2 can be the same or different and represent alkyl groups, preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, including substituted alkyl groups such as cyanoalkyl or alkoxyalkyl groups, aryl groups, preferably aryl groups having 6 to 20 carbon atoms, more preferably aryl groups having 6 to 10 carbon atoms or cyclic alkyl groups, preferably cyclic alkyl groups having 5 or 6 carbon atoms or R1 and R2 taken together represent the elements necessary to complete a cyclic amino group such as, for example, a piperidino, a morpholino, a pyrrolidino, a hexahydroazepino and a piperazino group, G represents an electron withdrawing group of any electron withdrawing groups known in the art such as, for example, CN, NO2, COOR or SO2R wherein R represents an alkyl groups known in the art such as
- the UV absorbing compounds for use in the silver halide photographic elements according to the present invention correspond to the general formula: in which: R1 represents an alkyl group having 1 to 10 carbon atoms, preferably a lower alkyl group having 1 to 4 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl group, and R3 represents an alkylene group having 1 to 10 carbon atoms whose carbon atom chain may comprise divalent groups such as, for example, -O-, -S-, -COO- or -SO2-.
- the UV absorbing compounds of the photographic elements according to the present invention have a strong absorption in the region of the electromagnetic spectrum at the boundary between the UV and the visible region.
- the UV absorbing compounds according to this invention have a peak or plateau in its absorbing spectrum around 380 nm. At least 80% of their absorption is in the range of from 350 to 400 nm, their absorption below 350 nm being such as not to affect significantly the response of the silver halide emulsion to the UV radiation of the exposure light, preferably such as not to absorb more than 30% of the radiation emitted by exposure lamps having a maximum emulsion wavelength of 317nm.
- the UV absorbing compounds of the photographic elements according to the present invention are highly soluble in water, so that they can be washed out of the element during processing, without a significant retention of UV absorption.
- the absorption of the element in D min areas after processing is, in the range from 300 nm to 400 nm, less than 0.10.
- the UV absorbing compounds of this invention can be prepared according to methods well known in the art.
- the UV absorbing compounds of general formulas (I) and (II) can be prepared by treating an appropriate amine compound containing the water solubilizing group with an appropriate intermediate in an organic solvent at boiling temperature followed by usual techniques for isolating the compounds.
- Useful intermediates are for example described in U.S. Patent 4,045,229.
- the UV absorbing compounds are used in an aqueous penetrable binder layer hydrophilic colloidal layer on the backside of the base or support layer. Said backside layer is further from the exposure light source than the silver halide emulsion layer and on the opposite side of the base from the silver halide emulsion layer.
- the UV absorbing compounds may be added in the form of a water solution to the hydrophilic colloidal coating composition.
- the amount of the UV absorbing compounds used is generally about 0.02g/m2 or greater (preferably no more than 0.3g/m2).
- the antihalation dye should provide an absorbance between 350 and 400 nm (e.g., 375 nm) of at least 0.3, preferably at least 0.5, and more preferably at least 0.8.
- silver halide emulsions for use in the photographic elements according to this invention are preferably higher chloride silver halide emulsions. They preferably contain at least 50% mole and more preferably at least 75% mole of silver chloride. The higher the silver chloride content, the lower is the natural blue and visible light sensitivity, even if the UV radiation sensitivity remains high.
- the silver halide emulsions to be used in type photographic elements according to the present invention are emulsions wherein at least 75% by weight of all silver halide grains are silver halide grains wherein at least at 80% mole is silver chloride.
- the remaining silver halide, if any, will be silver bromide and/or silver iodide but the latter should normally be present in an amount not exceeding 10% mole.
- the spectral sensitivity is even more extended to visible region and it may be useful to combine the UV absorbing compounds according to this invention with dyes capable of absorbing visible radiations so that the photographic element can be safely handled in bright light conditions.
- the dyes include, for example, oxonol dyes, benzylidene dyes, and the like, which can be bleachable or washable during processing. Examples of useful dyes are described, for example, in U.S. patent 4,140,531.
- sensitizing dyes are used to extend the sensitivity of the emulsion to longer wavelengths of visible light.
- the high chloride silver halide emulsions it also appears to be desirable for the high chloride silver halide emulsions to have a relatively small grain size, e.g. a mean grain size of from 0.05 to 0.6 micron, the preferred grain size being in the range of from 0.05 to 0.3 microns and the most preferred being from 0.05 to 0.1 micron.
- the high chloride silver halide grains preferably have a cubic shape, but may have other shapes, such as octahedra, spheres, tabular shapes, etc.
- silver halides are preferably prepared in the presence of at least a doping metallic element of the 8th Group of the Periodic Table of Elements, such as rhodium, iridium and ruthenium, which acts as electron acceptor.
- Said doping element is preferably chosen among water-soluble iridium salts, water-soluble ruthenium salts, or water-soluble rhodium salts.
- Iridium salts include iridium and alkaline metal halides, such as potassium iridium (III) hexachloride and sodium iridium (III) hexabromide.
- Rhodium salts include rhodium halides, such as rhodium (III) trichloride and rhodium (IV) tetrachloride and rhodium and alkaline metal halides such as potassium rhodium (III) hexabromide and sodium rhodium (III) hexachloride. These salts may be added in a quantity of from 0.5x10 ⁇ 4 to 10x10 ⁇ 4 moles, and preferably from 2x10 ⁇ 4 to 7x10 ⁇ 4 moles per mole of silver halide.
- Gold compounds used for chemical sensitization, include alkali metal chloroaurates, chloroauric acid, gold sulfide, gold selenide, and the like. Said gold compounds are generally used in a quantity of from 1x10 ⁇ 6 to 10 ⁇ 4 moles per mole of silver halide.
- the UV sensitive silver halide emulsions of the photographic elements according to this invention may contain various other photographic additives wich include sensitizers, desensitizers, solarization accelerators, stabilizers, hardeners, coating aids, preservatives, matting agents, antistatic agents, and the like, as described, for example, in U.S. Patent 4,495,274.
- Gelatin is generally used as hydrophilic colloid for the silver halide photographic elements of the present invention.
- hydrophilic colloids gelatin derivatives, natural substances such as albumin, casein, agar-agar, alginic acid and the like, and hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrolidone, cellulose ethers, partially hydrolized polyvinyl acetate, and the like can be used in addition to or instead of gelatin.
- gelatin can be partially substituted with polymer latexes obtained by emulsion polymerization of vinyl monomers, such as polyethylacrylate latexes, to improve the physical characteristics of the photographic layers.
- Support bases used in the negative-acting silver halide photographic elements according to this invention can be any of the conventionally used support bases, such as glass, cloth, metal, film including for example cellulose acetate, cellulose acetate-butyrate, cellulose nitrate, polyester, polyamine, polystyrene, and the like, paper including baryta-coated paper, resin-coated paper, and the like.
- the silver halide photographic elements according to this invention may be used in the field of Graphic Arts for various purposes, such as, for example, for contacting, for reproduction, for making offset printing masters, as well as in radiography for special purposes, in electron photography, and the like, where high UV sensitivity is required together with low blue light sensitivity.
- the silver halide photographic elements according to this invention are highly UV sensitive and give high contrast and low minimum density (fog) when they are exposed with light rich in UV rays, and they can be handled in bright white room light.
- a silver halide emulsion containing 84 mole % chloride and 16 mole % bromide was prepared by adding simultaneously and under stirring, over a period of 25 minutes, with a double-jet technique, water solution B and water solution C to water gelatin solution A, said water solutions having the composition reported herein below.
- the gelatin solution was kept at constant temperature of 30°C.
- the addition rate of solution B was constant, while the addition rate of solution C varied such as to maintain the millivolt of the emulsion thus formed at a value of 120 ⁇ 2 mv measured with a specific electrode for Br ion and a reference electrode of the saturated Ag/AgCl type.
- the emulsion was then chemically sensitized with sodium thiosulfate and sodium gold chloride. At the end of the chemical sensitization a triazole stabilizer was added and the emulsion was prepared for coating with the addition of additional gelatin, coating surface active agents and formaldehyde hardener.
- the emulsion was then coated at a silver coating weight of 2.7g Ag/m2 onto a polyethylene terephthalate support base which was backed with green antihalation layers that had varying amounts of yellow, blue and UV dye as shown as explained in Table 1 and Figures 1 and 2.
- the resulting films were exposed through a 0-2, 20 cm continuus wedge.
- the exposing lamp was a violux 1500S UV lamp at a distance of 52 inches from the film plane.
- the exposed films were developed in 3M RDC developer for 20 sec at 40°C and fixed in 3M fix roll fixer.
- the dry etch test then consists of making contact exposures to the original of 1x, 2x, 4x, 6x, 8x, 10x, 12x, 14x and 16x the dot-for-dot exposure.
- the resulting dot enlargement is measured.
- Both the highlight, shadow and midtone are of importance with the objective being to obtain a very cbntrolled movement of all dot sizes and as large a movement as possible in the midtone and shadow before the highlights veil in.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US386631 | 1982-06-09 | ||
US38663189A | 1989-07-31 | 1989-07-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0411819A2 true EP0411819A2 (fr) | 1991-02-06 |
EP0411819A3 EP0411819A3 (en) | 1991-12-18 |
Family
ID=23526402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19900308153 Ceased EP0411819A3 (en) | 1989-07-31 | 1990-07-25 | White light handleable negative-acting silver halide photographic elements |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0411819A3 (fr) |
JP (1) | JPH0368935A (fr) |
CA (1) | CA2020382A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0525445A1 (fr) * | 1991-07-30 | 1993-02-03 | Minnesota Mining And Manufacturing Company | Eléments photographiques à halogénure d'argent travaillant en négatif ayant une latitude d'exposition étendue dans l'ultra-violet |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69517160T2 (de) * | 1995-06-06 | 2000-11-16 | Agfa Gevaert Nv | Photographische Materialien |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59101646A (ja) * | 1982-12-02 | 1984-06-12 | Konishiroku Photo Ind Co Ltd | 明室用ハロゲン化銀写真感光材料 |
EP0210409A2 (fr) * | 1985-07-11 | 1987-02-04 | Minnesota Mining And Manufacturing Company | Composés UV-absorbants 3-aminoallylidènemalonitriliques et des matériaux photographiques les contenant |
EP0219010A2 (fr) * | 1985-10-04 | 1987-04-22 | Fuji Photo Film Co., Ltd. | Matériaux photographiques à l'halogénure d'argent |
EP0295945A2 (fr) * | 1987-06-18 | 1988-12-21 | Konica Corporation | Matériau photographique négatif à l'halogénure d'argent sensible à la lumière manipulable à la lumière du jour |
EP0300257A2 (fr) * | 1987-07-21 | 1989-01-25 | Minnesota Mining And Manufacturing Company | Eléments photographiques positif-directs à l'halogénure d'argent manipulables en lumière blanche |
-
1990
- 1990-07-04 CA CA 2020382 patent/CA2020382A1/fr not_active Abandoned
- 1990-07-25 EP EP19900308153 patent/EP0411819A3/en not_active Ceased
- 1990-07-30 JP JP20236290A patent/JPH0368935A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59101646A (ja) * | 1982-12-02 | 1984-06-12 | Konishiroku Photo Ind Co Ltd | 明室用ハロゲン化銀写真感光材料 |
EP0210409A2 (fr) * | 1985-07-11 | 1987-02-04 | Minnesota Mining And Manufacturing Company | Composés UV-absorbants 3-aminoallylidènemalonitriliques et des matériaux photographiques les contenant |
EP0219010A2 (fr) * | 1985-10-04 | 1987-04-22 | Fuji Photo Film Co., Ltd. | Matériaux photographiques à l'halogénure d'argent |
EP0295945A2 (fr) * | 1987-06-18 | 1988-12-21 | Konica Corporation | Matériau photographique négatif à l'halogénure d'argent sensible à la lumière manipulable à la lumière du jour |
EP0300257A2 (fr) * | 1987-07-21 | 1989-01-25 | Minnesota Mining And Manufacturing Company | Eléments photographiques positif-directs à l'halogénure d'argent manipulables en lumière blanche |
Non-Patent Citations (2)
Title |
---|
* abstract * * |
JAPANESE PATENTS GAZETTE Week 8429, 29 August 1984 Derwent Publications Ltd., London, GB; Page 16, AN 84-18& JP-A-59 101 646 (KONISHIROKU PHOTO KK) 12 June 1984 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0525445A1 (fr) * | 1991-07-30 | 1993-02-03 | Minnesota Mining And Manufacturing Company | Eléments photographiques à halogénure d'argent travaillant en négatif ayant une latitude d'exposition étendue dans l'ultra-violet |
US5316901A (en) * | 1991-07-30 | 1994-05-31 | Minnesota Mining And Manufacturing Company | Negative-acting silver halide photographic elements having extended UV exposure latitude |
Also Published As
Publication number | Publication date |
---|---|
EP0411819A3 (en) | 1991-12-18 |
CA2020382A1 (fr) | 1991-02-01 |
JPH0368935A (ja) | 1991-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4803150A (en) | Radiographic element exhibiting reduced crossover | |
EP0264288B1 (fr) | Eléments photographiques pour scanner à contraste élevé utilisant du ruthénium et de l'iridium comme dopant | |
EP0276566B1 (fr) | Elément radiographique à effet interimage réduit | |
EP0383055B1 (fr) | Elément photographique à haut contraste | |
KR950004964B1 (ko) | 사진 화상을 얻는 방법 및 그 엘리먼트 | |
US4849326A (en) | White light handeable direct-positive silver halide photographic elements | |
US4078937A (en) | Process for sensitizing a fine grain silver halide photographic emulsion | |
US3816121A (en) | Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group | |
JPH0612427B2 (ja) | 写真銀錯塩拡散転写反転法 | |
EP0300258B1 (fr) | Eléments photographiques comprenant des émulsions sensibles à la lumière au bromoiodure d'argent | |
US5213954A (en) | White light handleable negative-acting silver halide photographic elements | |
EP0411819A2 (fr) | Elément photographique à l'halogénure d'argent travaillant en négatif manipulable À la lumière du jour | |
US5316901A (en) | Negative-acting silver halide photographic elements having extended UV exposure latitude | |
JPH0675342A (ja) | 輻射線検出要素 | |
EP0398600B1 (fr) | Emulsions à l'halogénure d'argent dopé à sensibilité et contraste augmentés | |
JP2892832B2 (ja) | 写真スピード感度低下用の吸収層を有する写真記録材料 | |
JPH03163440A (ja) | 熱現像性感光材料 | |
SU464135A3 (ru) | Фотографическа эмульси | |
US5882846A (en) | Infrared sensitive photographic elements | |
EP0587230A2 (fr) | Colorants-filtres pour applications avec traitement rapide | |
DE3406246A1 (de) | Photographisches, lichtempfindliches silberhalogenidmaterial | |
US6235457B1 (en) | Arylidene compound, azomethine compound and silver halide photographic material | |
JP2794248B2 (ja) | 焼出し性のあるハロゲン化銀写真感光材料 | |
CA2054716A1 (fr) | Films positifs directs | |
EP0536647A1 (fr) | Matériaux photographiques positifs directs à l'halogénure d'argent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE CH DE FR GB IT LI NL |
|
17P | Request for examination filed |
Effective date: 19910102 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE CH DE FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19940908 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 19970302 |