US3816131A - Photographic dry copying process - Google Patents

Photographic dry copying process Download PDF

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US3816131A
US3816131A US00174270A US17427071A US3816131A US 3816131 A US3816131 A US 3816131A US 00174270 A US00174270 A US 00174270A US 17427071 A US17427071 A US 17427071A US 3816131 A US3816131 A US 3816131A
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image
producing compound
sensitizer
light
receiving layer
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Koenig A Von
H Ohlschlager
H Kampfer
J Gotze
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/46—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/10—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/64—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • 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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor

Definitions

  • the invention relates to a photographic dry copying process and to a light-sensitive material for carrying out this process.
  • Dry photographic processes for producing copies of an original are already known per se.
  • the materials used for these processes are usually materials which contain layers that are sensitive to light or heat. These layers are exposed imagewise to light or heat, which initiates a color-producing reaction and which leads to formation of the image.
  • the finished copies are still sensitive to light, and stabilization of these copies to daylight can generally only be achieved by a complicated aftertreatment.
  • Processes for the production of copies by imagewise exposure of a light-sensitive layer which contains a light-sensitive compound and an image-producing compound which can be transferred to an imagereceiving layer are also known.
  • the image-producing compound is converted in the exposed areas into a non-transferable compound.
  • the exposed layer is brought into contact with an image-receiving layer which contains compounds which react with the image-producing compound to form colored compounds, and the layers are heated while in contact with each other to a sufficiently high temperature, the image-producing compound from the unexposed areas of the light-sensitive layer is transferred to the image-receiving layer.
  • One such process is the so-called heat development process in which light-sensitive materials having a silver halide emulsion layer which contains a photographic developer substance, are used. After exposure, development is carried out by heating the lightsensitive material in contact with an image-receiving layer which contains substances, that react with the developer substance to produce dyes. The developer substance in the unexposed areas of the light-sensitive layer is transferred by the heat into the image-receiving layer so that a colored image is produced in these areas of the receiving layer.
  • a process which belongs to this type of copying process is described in U.S. Pat. No. 3,094,417 and uses light-sensitive layers which contain a transferable compound and a dye.
  • the transferable compound (4-methoxy-l-naphthol) is converted into a non-transferable product.
  • This compound is transferred by subsequent heating from the unexposed areas into an image receiving layer where it reacts with a silver salt (silver behenate) to produce a colored positive image.
  • the last mentioned process has the disadvantage that the sensitivity of the layers is relatively low and, moreover, the keeping quality of the material is limited.
  • a process for the production of copies by imagewise exposure of a light-sensitive layer which contains a sensitiser and an image-producing compound transferrable to an image-receiving layer the image-producing compound in the exposed areas being converted into a non-transferable compound and the exposed layer being brought into contact with an image-receiving layer which contains compounds which react with the image-producing compounds to fomi colored compounds and the layers which are in contact with each other being heated to a temperature at which the image-producing compound in the unexposed areas of the light-sensitive layer is transferred to the image-receiving layer, wherein the light-sensitive layer contains, as sensitizers, halogenated methine dyes of the formulae shown below, and, as image-producing, transferable compound, a reducing agent which is transferable at a temperature of between C and 200C and which is converted into non-volatile reduction productsupon exposure.
  • R 1) a saturated or unsaturated aliphatic group having preferably up to six carbon atoms which may be substituted, eg with halogen such as chlorine or bromine or with phenyl, hydroxyl, amino, carboxyl, sulfo, sulfamino, sulfamoyl, carboxylamino, carbamoyl, alkoxycarbonyl, alkoxy, aroxy, carboxyalkyl, sulfato or thiosulfato groups;
  • halogen such as chlorine or bromine or with phenyl, hydroxyl, amino, carboxyl, sulfo, sulfamino, sulfamoyl, carboxylamino, carbamoyl, alkoxycarbonyl, alkoxy, aroxy, carboxyalkyl, sulfato or thiosulfato groups
  • cycloalkyl such as cyclohexyl, or 3) aryl, in particular a group of the phenyl series;
  • R hydrogen, alkyl having preferably up to three carbon atoms, aryl such as phenyl, or cycloalkyl such as cyclohexyl;
  • R and R may be the same or different and represent hydrogen or hydroxyl but at least one is a hydroxyl group;
  • R hydrogen, alkyl or alkoxy having preferably up to five carbon atoms, halogen, in particular chlorine,, bromine or iodine, trifluoromethyl or aryl, especially a phenyl group;
  • R aryl such as phenyl, heterocyclic rings such as thienyl, or furyl, which may also be substituted;
  • X the ring members required to complete a benzene or naphthalene ring which contains at least one halogen such as Cl, Br or 1, or trifluoromethyl;
  • Z and Z hydrogen, alkyl having preferably up to three carbon atoms or alkoxycarbonyl groups having preferably up to four carbon atoms;
  • Z and Z may also together represent the methylene groups required to complete a S-membered or 6- membered ring;
  • any anion e.g. halide such as chloride, bromide or iodide, perchlorate, sulfate, methyl sulfate, p-toluene sulfate and the like; the anion is absent in cases where R contains an acid group in the anionic form so that a betaine is present;
  • D the ring members required to complete an isocyclic or heterocyclic ketomethylene ring; these rings may be the usual ketomethylene rings of cyanine chemistry, for example those of the rhodanine series such as 3-ethyl rhodanine, 3-allyl rhodanine or 3-cyclohexyl rhodanine, those of the 2-thio-2,4- oxazolidinedione series such as 3-ethyl-2-thio-2,4- oxazolidinedione.
  • rhodanine series such as 3-ethyl rhodanine, 3-allyl rhodanine or 3-cyclohexyl rhodanine
  • 2-thio-2,4- oxazolidinedione series such as 3-ethyl-2-thio-2,4- oxazolidinedione.
  • heterocyclic rings may contain a condensed benzene or naphthalene ring and other substituents; the heterocyclic rings may be the usual heterocyclic rings of cyanine chemistry, for example those of the thiazole series (e.g.
  • thiazole 4- methylthiazole, S-methylthiazole, 4,5- dimethylthiazole, 4-phenylthiazole, 5- phenylthiazole, 4,5-diphenylthiazole, benzothiazole, 4-ch1orobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 6- bromobenzothiazole, 5-iodobenzothiazole, 6- iodobenzothiazole, 4-methylbenzothiazole, 5- methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 4- phenylbenzothiazole, 5phenylbenzothiazole, 6- phenylbenzothiazole, S-hydroxybenzothiazole, 6- hydroxybenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S
  • oxazole 4-methyloxazole, 4- phenyloxazole, 4,5-diphenyloxazole, benzoxazole, S-chlorobenzoxazole, 6-chlorobenzoxazole, 5,6-dimethylbenzoxazole, 5-phenylbenzoxazole, S-hydroxybenzoxazole, S-methoxybenzoxazole, 5- ethoxybenzoxazole, 6-dialkylaminobenzoxazole, 5-carboxybenzoxazole, 5-sulphobenzoxazo1e, 5-sulphonamido-benzoxazole, S-B-carboxyvinylbenzoxazole, naphtho-(l,2-d)oxazole, naphtho (2,l-d)oxazole or naphtho-(2,3-d)oxazole), those of the imidazole series (e.g.
  • l-methylimidazole lethyl-4-phenylimidazole, 1-butyl-4,5- dimethylimidazole, etc.
  • l-methylbenzimidazole l -butyl-4-methylbenzimidazole, l-ethyl-S ,6- dichlorobenzimidazole, l-ethyl-5-trifluoromethylbenzimidazole, l-methylnaphth0-( 1 ,2-d)imidazole or lethylnaphtho-(2,3-d)imidazole), those of the 3,3-dialkylindolenine series (e.g.
  • phenylpyridine etc. those of the 4-pyridine series (e.g. Z-methylpyridine, 3-methylpyridine, 2,3- dimethylpyridine, 2,6-dimethylpyridine, 2- hydroxypyridine, quinoline, 3-methylquinoline, 5-
  • dihydroisoquinoline those of the thiazoline series (e.g. thiazoline, 4-methylthiazoline, etc.), and those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine series.
  • thiazoline series e.g. thiazoline, 4-methylthiazoline, etc.
  • pyrroline tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine series.
  • the heterocyclic rings and aryl groups may be further substituted in any manner, e.g.
  • alkyl groups which preferably have up to three carbon atoms, such as methyl or ethyl, or with halogen such as chlorine, bromine or iodine, the trifluoromethyl group, hydroxyl, alkoxy preferably with up to three carbon atoms such as methoxy or ethoxy, hydroxyalkyl, alkylthio, aryl such as phenyl or aralkyl such as benzyl, amino, substituted amino and the like.
  • the mono-, triand penta-methine cyanines of formula I may be synthesized by known methods (see e.g. F.M. Hamer The Cyanine Dyesand Related Compounds, 1964).
  • the dyes of formulae II to V are obtained by condensing 2-methyl quaternary salts of heterocyclic bases or ketomethylene compounds with theappropriate aldehydes in solventssuch:asalcohol, pyridine or glacial acetic acid to which is addeda base such as triethylamine or piperidine.
  • the image-producing compounds must meet the following conditions:
  • Phenols-and naphthols especiallycompounds-of the benzene'and'naphthalene series containing'atleast two :aromatic l'hydroxyl igroupswhich may :be partly .etheritied such as l hydroxy-4-alkoxy naphthalenes, or which are substituted with hydroxyl and an amino group or a substituted amino 1 group which :in .the case of benzene derivatives are situated in the :paraor orthoeposition, e.g.
  • R represents hydrogen, alkyl or aryl which may be substituted, for example with lower alkyl or alkoxy or with halogen
  • R ,R,R and R represent hydrogen, alkyl, aryl or a substituted alkyl or aryl group.
  • 3-Pyrazolidones may also be prepared by the process described in British Patent Specification No. 703,669, the end products being obtained by the direct condensation of esters of acrylic acid or derivatives thereof with hydrazines. This process is particularly suitable for reaction with hydrazine itself.
  • the 3-pyrazolidones thus obtained which have an oily consistency, can be ob tained in the form of crystalline compounds by converting them into salts, e.g. hydrochlorides, sulfates or naphthalene-l,5-disulfonates.
  • salts e.g. hydrochlorides, sulfates or naphthalene-l,5-disulfonates.
  • the preparation of the 4,4-dialkyl-3-pyrazolidones has been described in US. Pat. No. 2,772,282. In this process, 2,2-dialkyl-B- chloropropionic acid chlorides are reacted with hydrazines.
  • 3-Pyrazolidones may be used as free bases or in the form of their salts.
  • N,N-dialkylphenylene diamine derivatives especially those in which the alkyl groups contain preferably up to three carbon atoms and the phenylene nucleus may be substituted by alkyl or alkoxy groups.
  • the free primary amino group may be blocked, for example in the form of a Schiffs base by reacting it with aldehydes, especially benzaldehyde, or it may be blocked by a sulfomethyl group which may be introduced by a Mannich reaction.
  • aldehydes especially benzaldehyde
  • a sulfomethyl group which may be introduced by a Mannich reaction.
  • the phenylene diamine derivatives which have a blocked primary amino group are particularly suitable because stable layers can easily be produced by means of these compounds.
  • N,N-diethyl-p-phenylene diamino sulfate N,N'-dibenzylidene-p-phenylene diamine, N,N-diethyl-N'-sulfomethyl-p-phenylene diamine, N,N-dimethyl-N-sulfomethyl-p-phenylenediamine, 3-methyl-4-sulfomethylamino-N,N-diethylaniline, N-benzylidene-N',N-diethyl-p-phenylene diamine, 3-methoxy-4-sulfomethylamino-N,N-diethylaniline.
  • the image-producing substances of the type shown above are known per se.
  • aryl especially a group of the phenyl series, and the aryl ring may itself be substituted, e.g. with alkyl or alkoxy which preferably contains up to three carbon atoms, nitro, halogen such as fluorine, chlorine or bromine, amino, substituted amino groups, e.g. alkylated amino groups, (4) a heterocyclic group, e.g. benzothiazolyl, or (5) cycloalkyl such as cyclohexyl or cyclopentyl; R 1) hydrogen,
  • a saturated or olefinically unsaturated aliphatic group having preferably up to six carbon atoms which aliphatic group may be substituted, e.g. with phenyl as in the case of a benzyl or phenylethyl, with halogen such as fluorine, chlorine or bromine, with alkoxycarbonyl, with hydroxyl or alkoxy, (3) aryl, especially a group of and the phenyl series, the aryl ring may be substituted, e. g. with alkyl or alkoxy which preferably has up to three carbon atoms, with nitro or with halogen such as chlorine or bromine,
  • cycloalkyl such as cyclohexyl or cyclopentyl
  • R and R taken together may stand for the members required for completing a 5- or 6- membered carbocyclic or heterocyclic ring.
  • Suitable compounds are shown in the following table where for the first 33 listings R is hydrogen.
  • R 32 (1) hydrogen
  • a saturated or olefinically unsaturated aliphatic group having preferably up to six carbon atoms which may be substituted, e.g. with phenyl as in the case of benzyl or phenylethyl groups, with halogen such as chlorine or bromine, with cyano or with alkoxy, alkoxycarbonyl or anilinocarbonyl, (3) aryl, especially a group of the phenyl and series, the aryl ring may be substituted, e.g.
  • alkyl or alkoxy which preferably has up to three carbon atoms, nitro or cyano
  • an amino group which may be substituted, eg with alkyl which has preferably up to three carbon atoms, cycloalkyl, phenyl or acyl and especially acyl groups of short chain aliphatic carboxylic acids,
  • alkoxy having preferably up to three carbon atoms
  • R hydrogen or a 4-aminophenylamino group or 4-dialkylaminophenylamino group.
  • the light-sensitive layers contain at least one sensitizer in quantities of 10 to 300 mg/m and one or more image-producing compounds in quantities of 0.02 to 0.5 g/m This range of concentrations has been found to be suitable although concentrations outside this range may, of course, be employed. The concentration depends mainly on the requirements of the given reproduction process.
  • sensitizers with image-producing reducing agents can be found by simple tests. Suitable test methods for this purpose will be described hereinafter. The choice of solvent and of the binding agent used for producing the light-sensitive layer is also important for obtaining optimum results. Particularly suitable combinations of the components used for any particular purpose can be determined by the usual tests well known to the ordinary skilled person.
  • sensitizer and image-producing compound may be suspended or dissolved in solvents and mixed with the binding agent and applied to the layer support.
  • the usual natural or synthetic film-forming polymers are suitable as binding agents for the light-sensitive layer, e.g. proteins, especially gelatin, cellulose derivatives, especially cellulose ethers, cellulose esters or carboxymethyl cellulose, alginic acid and its derivatives, starch ether or gallactomannane, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate or completely or partly saponified polyvinyl acetate or copolymers of vinyl acetate, for example with olefines such as ethylene or propylene and copolymers of momomers of acrylicor methacrylic acid or derivatives thereof such as esters, amides or nitriles, etc..
  • proteins especially gelatin, cellulose derivatives, especially cellulose ethers, cellulose esters or carboxymethyl cellulose, alginic acid and its derivatives, starch ether or gallactomannane
  • the lightsensitive layers may be used as self-supporting layers or applied to a support.
  • Suitable supports are e.g. paper, especially baryta-coated or polyolefinecoated, more particular polyethylenecoated paper and cellulose esters, e.g. cellulose triacetate, polyesters, especially those based on ethylene terephthalate, glass, etc.
  • the image receiving material advantageously consists of an image receiving layer applied to a suitable support.
  • Substantially the same substances as those described above for the light-sensitive material are suitable as binding agent for the image receiving layer or as the layer support.
  • the image receiving layer contains compounds which should be insensitive, or as restricted as possible in their sensitivity, to visible light under the conditions of the process of the invention, and which react with the transferred image producing compounds to form colored products. Numerous compounds have been found suitable for this purpose. Chemically, these compounds belong to a wide variety of classes so that their systematic chemical classification is not possible. However, suitable compounds or suitable combinations of an image producing compound arranged in the lightsensitive layer and of the reactant for the imageforming reaction in the image receiving layer can be sufficiently clearly defined by simple laboratory tests customarily employed in the art. Thus, for example, the two reactants must react when briefly heated for a few seconds to a temperature of between about 80 and 200C to form a stable dye. A second test must then be carried out to choose suitable image producing compounds. The purpose of this test is to show whether the image producing compound will react sufficiently rapidly with the light-sensitive azide on exposure to light, so that, when the mixture is heated after it has been exposed, it will not produce a colored compound with the reactant in the image receiving layer.
  • Heavy metal compounds especially compounds of metals of Groups Ill a V a and to Groups I b, II b, V] b, Vll b and Vlll of The Periodic Table e.g. compounds of the following heavy metals:
  • Salts of these metals with long chained aliphatic, carboxylic acids are especially suitable, e.g. nickel stearate, cobalt palmitate, iron stearate, and the addition compound of bismuth nitrate with amines such as triethanolamine. It is found to be especially suitable to use silver compounds which are substantially insensitive to light under the conditions of the copying process according to the invention, e.g. the silver salts described in U.S. Pat. No. 3,330,663, i.e.
  • the image consists of the particular metal and/or a reaction product of the transferred image producing compound.
  • the image-receiving layer may also contain oxidising agents and dye components which react imagewise with the transferred image-producing compound to yield dyes by oxidative coupling, e.g. the known color couplers of color photography which couple with oxidised phenylenediamine derivatives to yield dyes, or compounds which in their oxidised form react under oxidising conditions with e.g. pyrazolin-5-one compounds to yield colored coupling products.
  • Suitable reactants are e.g. the oxidation products of p-phenylene diamines or their derivatives which react with pyrazolin-S-one compounds to yield azomethine dyes of the type known in conventional color photography.
  • Diazonium salts which react with the transferred reducing agents, e.g. the aminophenols, aminonaphthols, phenylene 'diarnine derivatives or pyrazolin-S-one compounds to form a colored product. This reaction is similar in principle to that used in the known photographic diazo-type process.
  • Leucophthalocyanines are also suitable for use as reactants for the reaction which produces the image dye.
  • Leucophthalocyanines which have not or could not be prepared from finished phthalocyanines are known as phthalocyanine precursors. This term is used, for example, in the article by B. R. A. Brooks, J. G. Burt, B. F. Skiles and M. S. Whelen, J. Org. Chem. 24, page 383 (1959).
  • the term phthalocyano-metal complexes is used for the same type of materials for which in the present context the term *leucophthalocyanines" is used.
  • Leucophthalocyanines according to this definition are colorless or only slightly colored products in which the phthalocyanine structure is already completely formed, and which can be converted into phthalocyanines by a reduction process. In this reduction process, constituents which the leucophthalocyanine molecule contains in addition to phthalocyanine may also be split off.
  • leucophthalocyanines may be prepared e.g. by first preparing a phthalocyanine, e. g.
  • a phthalocyanine which is free from metal or CuPc (Pc phthalocyanine), NiPc, CoPc or ZnPc and then treating the phthalocyanine with additional ligands under oxidising conditions, or by heating a reaction mixture which is in itself suitable for the preparation of a phthalocyanine to a temperature slightly below that required for the preparation of the phthalocyanine, or by carrying out the reaction without the reduction potential required for formation of the phthalocyanine.
  • Leucophthalocyanines which contain metal are more suitable for this reaction because those which are free from metal are relatively unstable.
  • the highly stable and only slightly colored leuco cobalt phthalocyanines are especially suitable.
  • the leuco cobalt phthalocyanines which are described in Angewandte Chemie, 68, page 145 (1956), e.g. the phthalocyanine cobalt ethylene diamine complex.
  • ethylene diamine other diamines or polyamine may also be used as ligands, for example propylene diamine- (l,2), and -(l,3), monoethylpropylene diamine- 1,3), hydroxyethylethylene diamine, N-methyl-N- B-hydroxyethylpropylene diamine, N,N'- diethylethylene diamine, N,N-di-(,B-aminoethyl)- ethylene diamine, N,N'-di-(B-aminoethyl)- ethylene diamine or N,N-di-[B-(B-aminoethyU- aminoethyl1-amine or also monoamines such as 3- (2'-ethylhexyloxy)-propylamine-( 1) or stearylamine.
  • the solubility properties of the leuco-CoPc depend on the type of amine used in the molecule.
  • color-forming reactants can be eliminated altogether from the image-receiving layer.
  • image-producing compounds for example phenols or naphthols, which yield sufficiently colored compounds when heated alone or in the presence of atmospheric oxygen.
  • the image-receiving material used may be plain, uncoated paper.
  • the image-receiving layers may contain other additives which advantageously influence the color tone, contrast, stability, etc. of the copy.
  • Image-receiving layers of this type are already known and have been described, for example, in German Auslegeschrift Nos. 895,101; 1,003,577; 1,159,758; 1,004,043 and 1,165,410, in Dutch Patent Specification No. 277,086, in U.S. Pat. No. 3,335,006 and in Belgian Patent Nos. 614,064 and 609,057.
  • the image-receiving layers may also contain white pigments, e.g. zinc oxide, silicon dioxide or titanium dioxide as fillers, for improving the whites and for controlling the tendency of the layers to stick, and they may contain terpene resins and organic acids for improving the stability in storage.
  • white pigments e.g. zinc oxide, silicon dioxide or titanium dioxide
  • terpene resins and organic acids for improving the stability in storage.
  • the color tone of the images produced can be influenced e.g. with compounds of the l-(2H)- phthalazinone series; toners of this type have been described in U.S. Pat. Nos. 3,080,254 and 3,446,648. Additives which accelerate the reduction process in the image-receiving layer have also been found to be advantageous. Sterically hindered phenols such as 2,6-ditert-butyl-p-cresol, for example, are suitable for this purpose. Compounds of this type have been described in U.S. Pat. No. 3,218,166. The image tone and image density may also be improved by certain metal salts, e.g. copper-ll stearate. Metal ion image intensifiers of this kind and their application have been described in German Auslegeschrift No. 1,572,209.
  • the usual light sources may be used for exposing the light-sensitive layers according to the invention such as mercury lamps, quartz iodine lamps or incandescent lamps.
  • the spectral sensitivity of the light-sensitive material depends on the nature of the dye or of the combination of dye and reducing image producing compound.
  • Exposure may be either contact exposure, optical exposure or reflection exposure.
  • Transfer of the image-producing compounds from the unexposed areas of the light-sensitive layers to the image-receiving layer is performed by heating at temperatures of between 80 and 200C. Heating may be effected e.g. by passing the exposed light-sensitive layer in contact with the image-receiving layer over hot plates or rollers or by exposure to infra-red light. The most suitable temperature and heating time depend, of course, on the nature of the image-producing compound and can easily be determined by a few simple tests.
  • the material according to the invention may also be modified in that the image-receiving layer and lightsensitive layer may be combined on one support.
  • a transparent layer support on which the image-receiving layer e.g. a layer containing silver behenate dispersed in a copolymer of styrene or isobutylene, is applied first, and the lightsensitive layer, e.g. an ethyl cellulose layer which contains the sensitiser and the reducing agent, is then applied on the image-receiving layer.
  • the image-receiving layer e.g. a layer containing silver behenate dispersed in a copolymer of styrene or isobutylene
  • the lightsensitive layer e.g. an ethyl cellulose layer which contains the sensitiser and the reducing agent
  • the sensitivity of these light-sensitive layers can be advantageously increased or extended to other regions of the spectrum in a manner depending on the absorption of the compounds according to the invention by combining the dyes which are to be used according to the invention with dyes which can be reduced by a process of photoreduction, e.g. the dyes mentioned in U.S. Pat. No. 3,094,417, e.g. erythrosine.
  • the layer is dried in the usual manner.
  • the image-receiving material is prepared by grinding the following components in a ball mill for 6 hours:
  • the layer When dry, the layer contains about 0.2 g of silver per m in the form of silver behenate.
  • the light-sensitive material is exposed behind a 2 wedge to a 1000 Watt iodine quartz lamp from a distance of 30 cm for minutes.
  • the exposed layer is then brought into contact with the image-receiving layer and heated to a temperature of 125C for seconds or heated in an ordinary commercial heat development apparatus.
  • the results were compared using each of the above-listed dyes as well as the following non-halogenated dyes, and are shown in Table 5:
  • the layer is dried in the usual manner. Processing
  • the light-sensitive material is exposed through a positive transparent original to an ordinary 1000 Watt incandescent lamp (tungsten filament) at a distance of 5 to 10 cm for 30 seconds.
  • a text printed on ordinary paper may be used as original.
  • the exposure to reflected light which is necessary in this case should be carried out for a period of between 15 and 25 seconds under otherwise the same conditions.
  • the exposed layer is then brought into contact with the image-receiving layer described in Example 1 and the two layers are heated to a temperature of to C for 5 to 20 seconds or treated in an ordinary commercial heat development apparatus.
  • silver behenate used in the image-receiving layer in this case
  • other silver compounds may be used. e.g. silver stearate or silver salts of octadecylmercaptoacetic acid, 2-octadecylmercapto-5- carboxymethylmercapto-1,3,4-thiadiazole (as described in U.S. Pat. No. 3,330,663), etc.
  • the choice of suitable compounds depends on the purpose for which they are to be used and the required color of the image.
  • a light-sensitive layer is prepared from a solution of:
  • Image-receiving material A layer is prepared from a solution of:
  • a light-sensitive layer is prepared as in Example 3 from:
  • a layer is prepared on a paper support from:
  • a light-sensitive layer is prepared from a solution of:
  • EXAMPLE 6 Light-sensitive material as in Example 1.
  • Image-receiving Material 50 mg of a leuco cobalt phthalocyanine stearylamine complex prepared by the method described below are dissolved in 40 g of a 1.5 percent solution of polyvinyl acetate in acetone and 26 g of a 4 percent solution of cellulose acetate in acetone, cast on paper and dried.
  • the leuco-CoPc used was prepared as follows:
  • EXAMPLE 7 Light-sensitive material as in Example 1. Image-receiving Material An image-receiving material is prepared from:
  • the solution is neutralised with ammonia and cast on paper.
  • EXAMPLE 8 Light-sensitive material as in Example 1. Image-receiving Material l g of bismuth nitrate is shaken in a ball mill with 40 g of a 1.5 percent solution of polyvinyl acetate in acetone. and
  • Example 2 Processing is carried out as described in Example 2, but the image-receiving material is in this case ordinary writing paper. A positive cyan image of the original is obtained.
  • Image-receiving Material Ammonia is added to a solution of 5 g of copper(ll) chloride in mlof H O until the precipitate which first forms redissolves, and 30 ml of 5 percent aqueous polyvinyl alcohol are then added. The solution is then cast on paper and dried.
  • EXAMPLE l 1 When used in combination with other dyes, e.g. erythrosine which has its sensitivity at 540 nm, the dyes listed in the following table extend the range of sensitivity of the light-sensitive material to the blue or red region of the spectrum.
  • other dyes e.g. erythrosine which has its sensitivity at 540 nm
  • a set of interference filters is used to determine the spectral sensitivity of the light-sensitive material.
  • the filters are permeable to the following wavelengths:
  • the light-sensitive material is exposed behind the in- I R2 AHIOIU).
  • the imagereceiving layer contains the silver salt of a long chain aliphatic carboxylic acid having eight to ,24 carbon atoms.
  • the imagereceiving layer contains a silver saltof a thioethersubstituted aliphatic carboxylic acid.
  • a light-sensitive photographic layer containing a sensitizer and an image-producing compound which can be transferred to an image-receiving layer at temperatures of between and 200C but which is converted by exposure into a nontransferable reaction product in the presence of the sensitizer, the improvement wherein the sensitizer has the formulae:
  • Z and Z separately hydrogen, alkyl or alkoxycarbonyl, or together stand for the methylene groups 25 required for completing a S-membered or 6- membered ring;
  • sensitizer is a polymethine dye which contains at least one iodine atom.

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076530A (en) * 1975-05-07 1978-02-28 Fuji Photo Film Co., Ltd. Dry photographic copying method for producing Te images
US4996141A (en) * 1988-01-13 1991-02-26 Ilford Limited Monomethine compounds
WO2000071517A1 (fr) * 1999-05-24 2000-11-30 Mitsubishi Pharma Corporation Compose de phenoxypropylamine
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions
US20070195127A1 (en) * 2006-01-27 2007-08-23 President And Fellows Of Harvard College Fluidic droplet coalescence
US20100143593A1 (en) * 2008-12-09 2010-06-10 Seiko Epson Corporation Image recording method, recorded matter, and image recording system
WO2011030927A1 (ja) * 2009-09-14 2011-03-17 住友化学株式会社 ３型１７β－ヒドロキシステロイドデヒドロゲナーゼを阻害するための化合物

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Publication number Priority date Publication date Assignee Title
CH660595A5 (de) * 1984-09-27 1987-05-15 Ciba Geigy Ag Cyaninfarbstoffe, verfahren zu ihrer herstellung und ihre verwendung als sensibilisatoren in photographischen materialien.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619237A (en) * 1969-03-10 1971-11-09 Nashua Corp Copy sheet utilizing certain acetoacetonitriles

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619237A (en) * 1969-03-10 1971-11-09 Nashua Corp Copy sheet utilizing certain acetoacetonitriles

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076530A (en) * 1975-05-07 1978-02-28 Fuji Photo Film Co., Ltd. Dry photographic copying method for producing Te images
US4996141A (en) * 1988-01-13 1991-02-26 Ilford Limited Monomethine compounds
WO2000071517A1 (fr) * 1999-05-24 2000-11-30 Mitsubishi Pharma Corporation Compose de phenoxypropylamine
US6720320B2 (en) 1999-05-24 2004-04-13 Mitsubishi Pharma Corporation Phenoxypropylamine compounds
US7196199B2 (en) 1999-05-24 2007-03-27 Mitsubishi Pharma Corporation Phenoxypropylamine compounds
US20050053864A1 (en) * 2003-09-05 2005-03-10 Rolf Dessauer Phthalocyanine precursors in infrared sensitive compositions
US20070195127A1 (en) * 2006-01-27 2007-08-23 President And Fellows Of Harvard College Fluidic droplet coalescence
US20100143593A1 (en) * 2008-12-09 2010-06-10 Seiko Epson Corporation Image recording method, recorded matter, and image recording system
WO2011030927A1 (ja) * 2009-09-14 2011-03-17 住友化学株式会社 ３型１７β－ヒドロキシステロイドデヒドロゲナーゼを阻害するための化合物

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CH581333A5 (enrdf_load_stackoverflow) 1976-10-29
FR2103502A1 (enrdf_load_stackoverflow) 1972-04-14
GB1353810A (en) 1974-05-22

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