US3615547A - Photographic light sensitive elements containing ultraviolet materials - Google Patents

Photographic light sensitive elements containing ultraviolet materials Download PDF

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Publication number
US3615547A
US3615547A US720344A US3615547DA US3615547A US 3615547 A US3615547 A US 3615547A US 720344 A US720344 A US 720344A US 3615547D A US3615547D A US 3615547DA US 3615547 A US3615547 A US 3615547A
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United States
Prior art keywords
layer
group
photographic light
light sensitive
sensitive element
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
US720344A
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English (en)
Inventor
Hiroyuki Amano
Fumihiko Nishio
Nobuo Tsuji
Kazuo Shirasu
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3615547A publication Critical patent/US3615547A/en
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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
    • G03C1/76—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
    • G03C1/8155—Organic compounds therefor

Definitions

  • the present invention relates to a photographic light-sensitive element containing an ultraviolet absorbent and, more particularly, to a photographic light-sensitive element having improved resistance to ultraviolet rays, resistance to staining, and an improved fluorescent-whitening effect.
  • an ultraviolet inhibitor in photographic emulsion layers, intermediate layers, protective layers, undercoats, or backing layers.
  • many of the conventional ultraviolet inhibitors have faults, i.e. the ultraviolet inhibitor itself is photodegraded by ultraviolet light to form undesirable stains.
  • the greater part of the ultraviolet inhibitor thus incorporated is dissolved out of the emulsion layer by photographic processing or washing, thereby resulting in a reduction or weakening of the ultraviolet inhibitor.
  • a fluorescent whitening agent which emits purple to blue fluorescence under ultraviolet radiation in a photographic emulsion layer (including incorporation in a positive layer for a printing paper utilized in a diffusion transfer reversal method) or in subsidiary layers, such as an undercoat, a protective layer or the baryta layer of a barytacoated paper.
  • fluorescent whitening agents are usually low molecular weight compounds, they have inherent faults. Often, the dying power of conventional fluorescent whitening agents with gelatin is very weak, and when they are incorporated into photographic gelatino-emulsion layers or subsidiary gelatin layers, the greater part of the fluorescent whitening agent will be dissolved out of the layers during photographic processing or water washing. This will, of course, reduce the whitening effect of these materials.
  • an object of the present invention is to provide a photographic light sensitive element which illustrates animproved ultraviolet inhibiting effect and an improved stain preventing effect without the aforesaid faults.
  • a further object of this invention is to provide a photographic light sensitive element which contains an improved fluorescent whitening agent and which has an excellent whitening effect without the conventional faults heretofore described.
  • a photographic printing paper containing a high molecular weight compound having a repeating unit of general formula (l) or (2) in the photographic emulsion layers, an intermediate layer, a protective layer, a baryta layer or a backing layer of the printing paper will have excellent whiteness even after photographic processing and washing.
  • a photographic light sensitive element produced in accordance with the present invention has at least one photographic emulsion layer, intermediate layer, a protective layer, represents a divalent hetero atom or a divalent hetero atomic subbing layer, backing layer or baryta layer which has incorgroup; m is or 1; and M represents an alkali metal or NH porated therein a high molecular weight compound having a repeating unit represented by general formula (1) or (2), which are as follows:
  • a high molecular weight compound having a repeating unit 5 represented by general formula l) or (2) which may be used in this invention has an excellent ultraviolet inhibiting effect, stain preventing effect and whitening effect.
  • R; g and it may be prepared by the following method using the raw M materials set out below.
  • R and R may each represent a hydrogen atom, an alkyl group p I having F8 carbon atoms an z zi 2 wherein R Y, Z and m have the'same meaning as indicated in carbon atoms a hydroxya lkyl group, r S the explanation of general formulas (l) or (2), These comcarbon atgms or such a group whlch 1S subsmute a su y ponents are reacted at a temperature of from about 50 to 150 group hfivmg from 14 carbon atoms or an alkali meta or an C. with the addition of from 2-2.4 mols of an aqueous sodium ammmum there; my rep?Sent 3 3mm hydroxide solution. in addition, the high molecular weight s 931755; n-
  • (1) or (2) of the high molecular weight compounds of this in- Examples of Y vention are as follows:
  • R may be, for example: CH3
  • N f I-NH Q-CH CHQ NH I [NH(CH NH 2 N N N N S O Na S 0 1% N N S OgNfl S Oa a 11 5 l H H CH5 CH3 Jn w F W OH OH]
  • a solution of 14.7 parts by weight of cyanuric chloride in 80 parts of acetone is dispersed in a slurry of 240 parts by weight of ice water, and the dispersion is maintained at about -3 C.
  • To the dispersion there is added dropwise l6.5 parts of sodium 4,4 diaminostilbene-2,2'-disulfonate as a aqueous solution.
  • hydrochloric acid is formed in the system, and an aqueous solution of sodium carbonate is added dropwise (4.2 parts by weight sodium carbonate and parts by weight water) so that the pH of the system is in the range of 4-5.
  • the system is, thereafter, stirred for about 30 minutes at about 05 C., and 7.5 parts of aniline is further added to the reaction mixture Thereafter, the temperature of the system is bonate (4.2 parts by weight sodium carbonate and 60 parts by weight water) is added gradually to the system.
  • the compound thus obtained is soluble in a dimethylformamide-water l:l solvent, and the intrinsic viscosity of the compound in the same solvent is 0.32 at 300 C
  • a higher molecular weight is desirable, but dissolution of the compound can be sufficiently prevented increased to 20 C. and an aqueous solution of sodium earif the degree of polymerization thereof is higher than 5 (a molecular weight greater than about 4,000).
  • photographic emulsion in this invention is defined to means the usual gelatino-silver halide light-sensitive emulsions, but synthetic resins such as polyvinyl alcohol and polyvinyl acetal may be effectively employed as protective colloids for the photographic emulsion, in addition to gelatin, in this invention.
  • photographic processing should be taken to mean standard development processes, such as stop fixing, washing, bleach fixing, washing, hardening, washing, and drying.
  • the intrinsic viscosity of each of the high molecular weight ultraviolet inhibitors of this invention in a dimethylformamide-water (1:1 solvent at 300 C. was in the range 0.1-2.0.
  • a red-sensitive silver chloro-bromide emulsion containing a cyan coupler (N-n-octadecyl-l-hydroxy-4-sulfo-2-l-naphthamide) was further applied to the greensensitive emulsion layer.
  • a protective layer was applied to the red-sensitive layer thus formed.
  • the thickness of the layers was approximately 2.0 microns.
  • the protective layer was formed by gradually adding g. of a 4% dimethylformamide-water (1:1) solvent solution of each of the high molecular weight ultraviolet inhibitors of this invention (1-14) to 1 kg. of an aqueous gelatin solution. This was applied and dried.
  • the color photographic printing paper thus prepared was exposed, developed in a developer containing N-ethyl-N-B- hydroxyethyl-phenylenediamine, and then subjected to stop fixing, washing, bleach fixing, washing, hardening, washing and drying.
  • the printing paper thus processed was then exposed to a xenon tester for 20 hours. Thereafter, the reduction ratio of each color at an image density of 1.0 was measured, the results of which are shown in the following table.
  • THe xenon tester used had a source with an energy distribution similar to that of sunlight.
  • the stain-preventing effect of the color photographic printing paper thus processed was measured, the results of which are shown in the following table.
  • the amount of staining is shown by the increase in the yellow component density of of unexposed portion of theprinting paper after exposing the printing paper to a xenon tester.
  • the whiteness of the color photographic printing paper was greatly improved when compared with a printing paper containing no such high molecular weight compound.
  • EXAMPLE 111 To 1 kg. units of the red-sensitive silver chlorobromide emulsion described in example 11 there was added 50 g. of a 4% dimethylformamide-water (1:1) solvent solution of each of the high molecular weight ultraviolet inhibitors of this invention (compounds 1-14). After uniform mixing, the described cyan coupler was added thereto. Then, utilizing the resulting silver halide emulsion and the blue-sensitive silver halide emulsion and the green-sensitive silver halide emulsion described in example 11,- a color photographic light-sensitive printing paper was prepared as in example 11.
  • the multiple layer printing paper thus prepared was exposed and subjected to development, stop fixing, washing, bleach fixing, washing, hardening, washing, and drying.
  • the printing paper thus processed was then exposed to a xenon tester for 20, hours, and the reduction ratio at a color image density of 1.0 wasmeasured, the results of which are shown in the following table.
  • a filter layer containing the high molecular compounds of this invention (Compounds l-l4) was formed on a film at a thickness of about 2.0 microns by the same procedures used in example I.
  • To the filter layer the blue-sensitive silver iodo-bromide emulsion containing the yellow coupler, the green-sensitive silver chloro-bromide emulsion containing the magenta coupler, and the red-sensitive silver chloro-bromide emulsion containing the cyan coupler were applied. Finally, a protective layer was applied to the red-sensitive emulsion layer.
  • This multiple layer-type light-sensitive film was exposed and subjected to development, stop fixing, washing, bleach fixing, washing, hardening, washing, and drying. Thereafter, the film thus processed was exposed, from the rear side of the film, to a xenon tester for 20 hours.
  • the reduction ratio at each color image density of 1.0 was measured, the results of which are shown in the following table.
  • the high molecular weight ultraviolet absorber of this invention was incorporated in both a protective layer on the uppermost red-sensitive emulsion layer and in an undercoat (or the backing layer), fading due to ultraviolet rays could be effectively prevented when the film was exposed from both sides.
  • a photographic light sensitive element comprising a sup port having thereon at least one layer containing a high molecular weight compound having a repeating unit selected from the group consisting of l S OaM R R, R,
  • R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl group having from 1-8 carbon atoms, an aryl group having 6-12 carbon atoms, a hydroxyalkyl group having 2-4 carbon atoms, a substituted hydroxyalkyl group having 2-4 carbon atoms, a sulfoalkyl group having 1-4 carbon atoms, an alkali metal salt of a sulfoalkyl group having l-4 carbon atoms and an ammonium salt of a sulfoalkyl group having l4 carbon atoms;
  • R represents a member selected from the group consisting of a halogen atom, OR, SR,
  • R and R each represents a member selected from the group consisting of (i) a hydrogen atom, (ii) an alkyl group having l-l 2 carbon atoms, a hydroxyalkyl group having 1-l2 carbon atoms, a sulfoalkyl group, an alkali salt of a sulfoalkyl group, an ammonium salt of a sulfoalkyl group, a carboxyalkyl group, an alkali metal salt of a carboxyalkyl group, an ammonium salt of a carboxyalkyl group, an aralkyl group; (iii) an aryl group having 6-l8 carbon atoms, a hydroxy derivative of an aryl group having 6-18 carbon atoms, a carboxy derivative of an aryl group having 6-18 carbon atoms, a sulfonic acid derivative of an aryl group having 6-l8 carbon atoms, an alkali metal salt of an aryl group having 6-18
  • R and R are selected from the group consisting of H, CH C H -C H -CH CH(CH zM OaMC l?) ill) where M and p have the same meaning as above, Y is a member selected from the group consisting of [(CH2),,] (CH2) (1 Where q may vary from 2 to 10,
  • COOM l A photographic light sensitive element as claimed in COOM', claim 1 wherein the layer is a photographic emulsion layer.
  • Q 8 A photographic light sensitive element as claimed in I claim 1 wherein the layer is a baryta layer. $03M 9.
  • WNH(CH NH YN z SO Na soiNa I 1155 N N N W IvlNHQ CH CHNH-
  • WINH-(CHQ NH 2 l N V some some 25 I l I M H17 CH3 CH3 n N N l-NHCH CHNH! m-NH(CH: NH

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Polyamides (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US720344A 1967-04-10 1968-04-10 Photographic light sensitive elements containing ultraviolet materials Expired - Lifetime US3615547A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2275667 1967-04-10

Publications (1)

Publication Number Publication Date
US3615547A true US3615547A (en) 1971-10-26

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Country Status (6)

Country Link
US (1) US3615547A (enrdf_load_stackoverflow)
BE (1) BE713440A (enrdf_load_stackoverflow)
DE (1) DE1772170A1 (enrdf_load_stackoverflow)
FR (1) FR1576417A (enrdf_load_stackoverflow)
GB (1) GB1227392A (enrdf_load_stackoverflow)
NL (1) NL6805137A (enrdf_load_stackoverflow)

Also Published As

Publication number Publication date
BE713440A (enrdf_load_stackoverflow) 1968-08-16
DE1772170A1 (de) 1970-08-06
DE1772170B2 (enrdf_load_stackoverflow) 1978-03-09
FR1576417A (enrdf_load_stackoverflow) 1969-06-23
NL6805137A (enrdf_load_stackoverflow) 1968-10-11
GB1227392A (enrdf_load_stackoverflow) 1971-04-07

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