US3728125A - Photographic light-sensitive material suitable for silver-dye bleaching method - Google Patents

Photographic light-sensitive material suitable for silver-dye bleaching method Download PDF

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Publication number
US3728125A
US3728125A US00065714A US3728125DA US3728125A US 3728125 A US3728125 A US 3728125A US 00065714 A US00065714 A US 00065714A US 3728125D A US3728125D A US 3728125DA US 3728125 A US3728125 A US 3728125A
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group
dye
silver
alkyl
emulsion
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US00065714A
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K Shiba
M Hinata
M Yoshida
S Watanabe
S Imai
A Sato
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances

Definitions

  • such a material comprises PHOTUGRAPHIC LIGHT-SENSIT VE MATERIAL on a support member a red-sensitive layer containing a FOR MINER-DYE BLEACHING cyan dye, a green-sensitive layer containing a magenta Keisuke Shiba, Masanao Hinata, Malroto Yoshida, 5 Y 9Y layer Capable decreasing the Shinichi Imai, Akita Sam, and Shigem Watanabe, trinsic sensitivity of the layers under the filter layer and Kamgawa, Japan assignors to Fuji Photo Film Co a blue-sensiuve layer containing a yellow dye as an upper- Ltd., Kanagawa, Japan most y No Drawing.
  • the sensitivity of the light-sensitive layer in the ABSTRACT OF THE DEC 15 silver-dye bleaching method is lower than that of other A light-sensitive silver halide emulsion containing a P P meth0d$- herefore, one of large difdye capable of being bleached in the silver dye bleaching ficllltlcs Present With h y f h h method 15 process and at least one sensitizing dye having the genp p r a l y r having suflicient sensitivity.
  • the sensitizing dye used in a light-sensitive R is selected from the group consisting of a hydrogen material for the silver-dye bleaching method must satisfy atom, an alkyl group, a substituted alkyl group, and an certain necessary conditions.
  • the sensitizing dye should aliphatic chain to be combined with the N of the heteronot have adverse influences upon the sensitivity and the cyclic ring containing Z wherein R, is selected from the stability of the emulsion, in particular, during storage. group consisting of a hydrogen atom, an alkyl and an Furthermore, the sensitizing dye should not result in color aryl group; wherein m, n, and p are 1 or 2, and a repremaining after processing of the photographic material.
  • the sensitizing dye Should be adsorbed a intramolecular salt i f d hen 1:1; and wherein fast on silver halide grains not so as to be substituted by Z and Z each is the non-metallic atomic group necessary a dye suitable for the s lver-dye bleaching method. Otherto complete a 5- or 6-membered heterocyclic ring, is dis wise, the sensitizing action is decreased by the presence of closed.
  • the emulsion can be super-sensitized by the adthe y sulta'hle t the Silva-dye bleaching methodditi f upersensifizing dye to th l i
  • the sensitizing dyes used hitherto in silver halide materials are not suitable for the silver-dye bleaching method.
  • the basic cyanine tends to be desorbed from the silver halide grains by a dye having a sull f th ton Fleld o e mven 1 fonate group, suitable for the silver-dye bleaching meth- ThlS lnvefltltfh re1atet0 the spfictfal FQnsltlZatlOn od.
  • Betaine cyanines may be used as the sensitizing dye photographic l ght-sens tive layer containing a dye suitfor a photographic layer in the Si1ver dye bleaching a'ble fOT 11Se Wlth the sllvef-dye bleachlng methodmethod, but often a slight coloring is retained therein.
  • the silver is removed to retain a dye layer SUMMARY OF THE INVENTION having a reverse gradation to that of the original silver A photographic light-sensitive layer suitable for the image.
  • the use of a multi-layer material having three narily high sensitivity is prepared by adding to a silver or more component color layers of sensitivity-differing halide emulsion containing a dye suitable for the silver spectrum regions is advantageous to obtain a multidye bleaching method, a sensitizing dye, as a sensitizer, colored photograph as in the case of the color developing represented by the following generally Formula I:
  • R, R R and R each represents alkyl, substituted alkyl, allyl, aralkyl, substituted aralkyl and aryl groups; wherein R represents a hydrogen atom, an alkyl group, a substituted alkyl group or an aliphatic chain to be combined with N in the heterocyclic ring containing Z wherein R represents a hydrogen atom, an alkyl group or an aryl group; wherein m, n and p represent respectively 1 or 2, and d represents 0, 1 or 2; wherein X represents an anion; and wherein Z and Z each represents the non-metallic atom groups necessary to complete a 5- or 6-membered heterocyclic ring.
  • R, R R and R in the general Formula I can be, for example, a methyl, an ethyl, a propyl, a fi-hydroxyethyl, a B-acetoxyethyl, a sulfato ethyl, a carboxymethyl, a fl-carboxyethyl, a 'y-carboxypropyl, a fi-sulfoethyl, a 'ysulfopropyl, a a-sulfobutyl, a vinyl-methyl, a benzyl, a phenethyl, a p-carboxbenzyl, a p-sulfophenethyl and a phenyl group.
  • R in the general Formula I can be, for example, a methyl, an ethyl or a phenyl group.
  • the substituted alkyl group R in the general Formula I can be, for example, a p-hydroxyethyl, a fl-acetoxyethyl or a B- aminoethyl group.
  • X in the general Formula I can be, for example, a chloride ion, a bromide ion, a perchlorate ion, a p-toluenesulfonate ion, a benzeuesulfonate ion, an ethylsulfate ion or a methylsulfate ion.
  • heterocyclic ring containing Z or Z in the general Formula I examples include thiazoles, such as thiazole and thiazoles having a methyl or a phenyl group in the ring; benzothiazoles, such as benzothiazole and benzothiazoles having nucleus substitutents such as a halogen atom, alkyl, alkoxy, and phenyl groups in the benzene ring; naphthothiazoles, such as u-naphthothiazole, flnaphthothiazole, tetrahydronaphthothiazole and naphthothiazoles having nucleus substituents such as an alkoxy group in any of the benzene rings; oxazoles, such as those having substituents such as alkyl and phenyl groups in the ring, benzoxazoles, such as benzoxazole and benzoxazoles having nucleus substituents such as a methyl
  • 2-pyrridine such as 2-pyridine and 2-pyridines having nucleus substituents (exclusive of the 2-position), such as a methyl group
  • 4-pyridines such as 4-pyridine
  • the sensitizing dye represented by the general Formula I I is a dye having four hetero radicals wherein two ketomethylene radicals are directly bonded, which can sensitize a silver halide emulsion strongly in the coexistence with the dye used in the silver-dye bleaching method. Since it gives a more excellent sensitivity even in the case of a small quantity of the dye added per g-mole of silver halide in comparison with the conventional basic cyanine dyes, any photographic layer containing it is substantially freed from color remaining after processing.
  • the sensitizing dye represented by the general Formula I can favorably sensitize an emulsion used in the silverdye bleaching method, containing a dye suitable for the silver-dye bleaching method, without any aid, but supersensitization of the sensitizing dye by a compound represented by the following general Formulae H or III is preferred.
  • Compound II has the general formula shown below:
  • R R R and R each represents a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, a substituted aryloxyl group, such as a phenoxyl, an o-toloxyl or a p-sulfophenoxyl group, a halogen atom, such as a chlorine or a bromine atom, a heterocyclic nucleus such as morpholinyl or piperidyl, an alkylthio group such as a methylthio or an ethylthio group, a heterocyclic thio group such as a benzothiazylthio group, an arylthio group, an unsubstituted or a substituted alkylamino group, such as a methylamino, an ethylamin
  • A represents A or A shown as follows and, in particular, at least one of R R R and R representing a substituent containing a SO M group when A is A OONHQGEEOHQNHCO-Ql A can he:
  • Compound III has the general formula shown below:
  • R represents an acylamino group, such as an acetamide, a sulfobenzamide, a 4-methoxy-3-sulfobenzamide, a 2-ethoxybenzamide, a 2,4-diethoxybenz amide, a p-toluylamino, a 4-methyl-Z-methoxybenzamide, a l-naphthylamino, a Z-naphthylamino, a 2,4-dimethoxybenzamide, a 2-phenylbenzamide, or a 2-thienylbenzamide group, or a sulfo group;
  • R represents an acylamino group, such as defined above for R and R represents a hydrogen atom or a sulfo group.
  • the compound having the general Formula III has at least one sulfo group.
  • the sensitizing dye represented by the general Formula I is used more favorably through supersensitization with a Novolak type condensate of a polyhydroxybenzene and formaldehyde.
  • polyhydroxybenzene is intended to cover substituted benzenes having from 1 to 3 hydroxyl groups on the benzene nucleus.
  • the Novolak type condensate of the polyhydroxybenzene and formaldehyde will hereinafter be referred to as the Formalin condensate.
  • polyhydroxybenzenes are represented by the following general Formulae IVa, IVb, IVc, IVd:
  • R and R each represents -OH, 0M, '-OR14: 'NH2, -NHR14, N(R14)2, and -NI-INHR with R representing an alkyl group of from 1 to 8 carbon atoms, an aryl group or an aralkyl group; M represents an alkali metal or an alkaline earth metal; X represents an Ol-I group or halogen atom; X; represents a halogen atom; n n n and n each reprno- C 118 N/ tiJzHs S e H3 Ha resents l, 2, or 3, except that n and n are equal to 3 at the same time.
  • the sensitizing dye of the invention represented by the general Formula I, is described in F. M. I-Iamer, Cyanine Dyes and Related Compounds Thereof, Sect. 15, p. 671, Interscience Publishers (1964).
  • the condensate of the polyhydroxybenzene can be synthesized according to the conventional synthesis method for phenol-formaldehyde resins of the Novolak type [(for example, as described in W. R. Sorenson, T. W. Campbell, Preparative Methods of Polymerchernistry, John Wiley and Sons, Inc. (1961)].
  • the polysubstituted hydroxybenzene is dispersed in water, heated after concentrated hydrochloric acid and 37% Formalin are added and held at C. for 30 minutes to 1 hour with agitation. Then, if necessary, hydrochloric acid is added further and the heating with agitation is continued. After the reaction, the reaction product is removed into cold water and the resultant precipitate can be purified.
  • the resulting precipitate is filtered, redissolved in 1,000 parts of methanol as it is not dried, and then precipitated with Water.
  • the reaction product is filtered and dried to obtain the product.
  • Other condensates can readily be obtained by using other polyhydroxybenzenes in place of the p-hydroxybenzoic acid in the abovedescribed method.
  • the condensation unit i.e., the degree of polymerization of the condensate obtained by the above described method is from 2 to 10 as with usual Novolak resins.
  • condensates having a condensation unit of from 2 to 10, preferably having a condensation unit of from 2 to 5 and a molecular weight of from 300 to 800 are suitable.
  • sensitizing dye used in the invention examples are given as follows, but without limiting the invention.
  • the sensitizing dye represented by the general Formula I is added to a photographic layer used in the silver-dye bleaching method With a dye suitable for the silver-dye bleaching method.
  • the sensitizing dye is preferably added to an emulsion before coating, and washed with water, before an azo dye is added.
  • a sensitizing dye to a photographic emulsions.
  • the dye is added to photographic emulsions in the form of a solution in water or an organic solvent, such as methanol or ethanol.
  • Suitable emulsions for use in this invention are silver halide, such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide or silver chloroiodobromide CO-NH OH 10 emulsions.
  • silver halide such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide or silver chloroiodobromide CO-NH OH 10 emulsions.
  • gelatino-silver halide emulsion is used in the invention, but cellulose derivatives and resinous materials which do not disturb light-sensitive materials can be used in place of the gelatin.
  • the photographic emulsion used in the invention can have conventional additives such as chemical sensitizers, fog inhibitors, stabilizers, hardeners, coating aids, plasticizers, development accelerators and air fog inhibitors.
  • the photographic emulsion can be coated onto a suitable support, such as a glass, a cellulose derivative film, a synthetic resin film, a laminated paper or a synthetic paper in any conventional manner.
  • a suitable support such as a glass, a cellulose derivative film, a synthetic resin film, a laminated paper or a synthetic paper in any conventional manner.
  • the dye used in combination with the sensitizing dye represented by the general Formula I is any dye used conventionally in the silver-dye bleaching method, preferably one containing a phenolic hydroxyl group or a sulfonate group.
  • Suitable dyes are described in Japanese patent publications 10,280/61, 9,587,/64 and 25,768/ 64, and in U.S. Pats. 3,211,554, 3,223,527, 3,264,109, 3,454,402, 3,178,291, 3,385,706, 3,455,695, 3,259,498, 3,244,525, 3,304,181, 3,322,543, 3,210,190 and 3,454,401.
  • Suitable dyes are, for example:
  • Hols son mo om Hols Hz (3H1 with R being a p-tolpenesulfone group or a 4-acetylaminobenzoyl group,
  • R being a benzoyl, a 4-acetylaminobenzoyl or a 4- benzoylaminobenzyl group.
  • EXAMPLE 1 HOsS the coated photographic layer was exposed through a step wedge of blue light (Latten Filter No. 478) and red light (Fuji Filter No. 7), developed and fixed. The development was carried out with the developer having the composition shown in Table 1 at 20 C. for 2 minutes.
  • anilino group an o-anisilamino group, a m-anisilamino group, a p-anisilamino group, an o-toluidino group, a mtoluidino group, a p-toluidino group, a p carboxyaniliho group, a hydroxyanilino group, a naphthylamino group,
  • R, R R and R each is selected from the group consisting of an alkyl group, an allyl group, an aralkyl group, an aryl group, a substituted alkyl group wherein said substituent is selected from the group consisting of hydroxy, acetoxy, sulfato, carboxy, sulfo and vinyl, and a substituted aralkyl group wherein said substituent is selected from the group consisting of sulfo and, carboxy, and wherein R is selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxy alkyl group, an acetoxy alkyl group, and an amino alkyl group, and an aliphatic chain to be combined with the N of the heterocyclic ring containing Z wherein R is selected from the group consisting of a hydrogen atom; an alkyl
  • R, R R and R are selected from the group consisting of methyl, ethyl, propyl, fl-hydroxyethyl, p-acetoxyethyl, sulfatoethyl, carboxymethyl, flcarboxyethyl, -carboxypropyl, fl-sulfoethyl, 'y-sulfopropyl, 6-su1fobutyl, vinylmethyl, benzyl, phenethyl, pcarboxybenzyl, p-sulfophenethyl, and phenyl groups; wherein the substituted alkyl group in R is selected from the group consisting of a fi-hydroxyethyl, aT'B-acetoxyethyl and a fl-aminoethyl group; and wherein the heterocyclic ring containing Z or Z;
  • the light-sensitive silver halide emulsion of claim 1 con tains additionally a condensate of a polyhydroxy benzene and formaldehyde.
  • the light-sensitive silver halide emulsion as having from 1 to 8 carbon atoms, an aryl group and an claimed in claim 1, wherein the dye capable of being aralkyl group; wherein M is selected from the group bleached out in the silver dye bleaching process is 43011111 (IJH H300 (13H H038 SOzH 6-011:
  • -A photographic light-sensitive element comprising wherein X is selected from the group consisting of an a support having thereon at least one layer containing the --OH and a halogen atom; wherein X is a halogen atom; 5 light-sensitive silver halide emulsion as claimed in claim 1. wherein n 11 n and n1 each are 1, 2 or 3, except that 14. The light-sensitive silver halide emulsion as claimed n and n are equal to 3 at the same time. in claim 1, wherein the dye capable of being bleached 8.
  • the supersensitized photographic emulsion as out in the silver dye bleaching process is selected from claimed in claim 7, wherein the condensate has a com the group consisting of SOBH bCHs SOaH Q-OCHN 11 0011, OH sumo-Q, NH:

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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US00065714A 1969-08-20 1970-08-20 Photographic light-sensitive material suitable for silver-dye bleaching method Expired - Lifetime US3728125A (en)

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JP44065827A JPS4933784B1 (enrdf_load_stackoverflow) 1969-08-20 1969-08-20

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JP (1) JPS4933784B1 (enrdf_load_stackoverflow)
BE (1) BE755063A (enrdf_load_stackoverflow)
CA (1) CA960503A (enrdf_load_stackoverflow)
CH (1) CH568583A5 (enrdf_load_stackoverflow)
DE (1) DE2041199A1 (enrdf_load_stackoverflow)
FR (1) FR2059023A5 (enrdf_load_stackoverflow)
GB (1) GB1324859A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877937A (en) * 1973-06-04 1975-04-15 Itek Corp Polyrhodanine sensitizers for organic photoconductors
US6022307A (en) * 1998-07-14 2000-02-08 American Cyanamid Company Substituted dibenzothiophenes having antiangiogenic activity

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877937A (en) * 1973-06-04 1975-04-15 Itek Corp Polyrhodanine sensitizers for organic photoconductors
US6022307A (en) * 1998-07-14 2000-02-08 American Cyanamid Company Substituted dibenzothiophenes having antiangiogenic activity

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CH568583A5 (enrdf_load_stackoverflow) 1975-10-31
BE755063A (fr) 1971-02-01
DE2041199A1 (de) 1971-03-25
CA960503A (en) 1975-01-07
GB1324859A (en) 1973-07-25
FR2059023A5 (enrdf_load_stackoverflow) 1971-05-28
JPS4933784B1 (enrdf_load_stackoverflow) 1974-09-10

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