DE1547640A1 - Improved Photographic Material - Google Patents
Improved Photographic MaterialInfo
- Publication number
- DE1547640A1 DE1547640A1 DE19671547640 DE1547640A DE1547640A1 DE 1547640 A1 DE1547640 A1 DE 1547640A1 DE 19671547640 DE19671547640 DE 19671547640 DE 1547640 A DE1547640 A DE 1547640A DE 1547640 A1 DE1547640 A1 DE 1547640A1
- Authority
- DE
- Germany
- Prior art keywords
- photographic
- compound
- contain
- group
- development
- 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.)
- Pending
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Classifications
-
- 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
- C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
-
- 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
- C07D239/56—One oxygen atom and one sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- 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
- C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
-
- 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
- C07D277/68—Benzothiazoles 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 in position 2
- C07D277/70—Sulfur atoms
- C07D277/74—Sulfur atoms substituted by carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
-
- 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
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- 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
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
-
- 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
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/156—Precursor compound
- Y10S430/158—Development inhibitor releaser, DIR
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
AGFA-GEVAERTAGAGFA-GEVAERTAG
1 5 4 7 6 Λ O1 5 4 7 6 Λ O
LEVERKUSENLEVERKUSEN
za/Hg :· 7. M 1967za / Hg: 7th M 1967
Verbessertes photographisches MaterialImproved Photographic Material
Die Erfindung betrifft ein photographisches Material mit verbesserten Eigenschaften, das Verbindungen enthält, die mit Bntwickleroxidationsprodukten unter Abspaltung von entwicklungshemmenden Substanzen reagieren.The invention relates to a photographic material with improved properties, which contains compounds with developer oxidation products with elimination of development-inhibiting substances react.
Das Prinzip, photographischen Schichten Substanzen zuzusetzen» die bei der Entwicklung bildmäÄig gespalten werden, wobei die Eigenschaften der ursprünglichen Substanz verändert werden und neue Substanzen mit neuen Eigenschaften bildmälig auftreten, ist seit langem bekannt.The principle of adding substances to photographic layers » which are visually split during development, with the Properties of the original substance are changed and new substances with new properties appear pictorially, has long been known.
Zu dieser Gruppe von Substanzen gehören z. B. die farbigenThis group of substances includes, for. B. the colored ones
Farbkuppler, die an der Kupplungsstelle eine farbige Azogruppierung enthalten, die an den belichteten Stellen bei der Reaktion mit dem Entwickleroxidationsprodukt abgespalten wird, wobei der Farbkupplerrest zu einem Farbstoff kuppelt, während der die Azogruppierung enthaltende Rest eliminiert wird. An den nicht belichteten Stellen bleibt dadurch der ursprünglicheColor couplers which have a colored azo group at the coupling point contain, which is split off at the exposed areas during the reaction with the developer oxidation product, wherein the color coupler moiety couples to a dye while the moiety containing the azo moiety is eliminated. At the unexposed areas remain the original
A-G 238 - 1 - AG 238 - 1 -
009849/1157009849/1157
Farbstoff zurück. An den belichteten Stellen entsteht ein
neuer Farbstoff.Dye back. A occurs in the exposed areas
new dye.
Es sind ferner Farbkuppler bekannt, die zwei Firbjcupplermoleküle
enthalten, wobei diese beiden Moleküle durcn Thioäther- oder Dithioätherbrücken an den Kupplungsstellen miteinander
verbunden sind. Diese Farbkuppler sind üffuaionsfest.
Bei der Entwicklung wird die Thioätherbrücke durch
Reaktion mit dem oxidierten Farbkuppler aufgespalten. Hierbei entsteht aus dem einen Molekülteil ein Farokuppler, der
durch Kupplung mit dem EntwicklercxidationsproduKt in einen
Farbstoff überführt wird; aus dem anderen ilolekülteil entsteht
eine mercaptogruppenhaltige Verbindung.Color couplers are also known which contain two company coupler molecules, these two molecules being connected to one another at the coupling points by thioether or dithioether bridges. These color couplers are ufuaion-proof. During the development, the thioether bridge is through
Reaction with the oxidized color coupler split. This creates a dye coupler from one part of the molecule, which is converted into a dye by coupling with the developer oxidation product; The other part of the molecule creates a compound containing mercapto groups.
Später wurden die obigen Reaktionsprinzipien angewendet, um FarbJcupplermoleküle über bestimmte Brilckenglieder mit Molekülen
zu verbinden, die entwicklungshemmende Wirkung haben. An den belichteten Stellen wird durch Reaktion mit Entwickleroxidationsprodukt
die Brückenbindung gespalten und es entsteht aus dem Farbkupplerteil des ursprünglichen Moleküls ein Farbstoff.
Gleichzeitig wird das entwicklungshemmende Molekül in Freiheit gesetzt. Dieses kann nun an den belichteten Stellen seine
Wirkung entfalten, wobei eine Verbesserung der photographischen Eigenschaften der lichtempfindlichen Silberhalogenidemulsion^
insbesondere eine Verflachung der Gradation und eine Verbesserung der Korngröße und damit der Schärfe erreicht wird. Aus diesen
Gründen sind derartige Verbindungen vorteilhaft. Ihre praktischeThe above reaction principles were later applied to link dye coupler molecules via certain bridge members with molecules that have a developmental inhibiting effect. At the exposed areas, the bridge bond is cleaved by reaction with developer oxidation product and a dye is created from the color coupler part of the original molecule.
At the same time, the development-inhibiting molecule is set free. This can now be in the exposed areas
Develop an effect, with an improvement in the photographic properties of the light-sensitive silver halide emulsion ^ in particular a flattening of the gradation and an improvement in the grain size and thus the sharpness is achieved. For these reasons, such connections are advantageous. Your practical
A-Q 238 -2. 909849/1157 AQ 238 - 2nd 909849/1157
Anwendung ist jedoch relativ kompliziert, da sie diffusionsfest eingelagert werden müssen und der Farbkupplerrest des Gesamtmoleküls sorgfältig ausgewählt und dosiert v/erden mul, um die Farbbalance des photographischen Materials zu erhalten. Wegen der strengen Anforderungen, die an die Absorptions-Eigenschaften des entstehenden Farbstoffes gestellt werden müssen, sind die Auswahlmöglichkeiten relativ gering.However, application is relatively complicated because it is diffusion-resistant must be stored and the remainder of the color coupler of the entire molecule must be carefully selected and dosed to maintain the color balance of the photographic material. Because of the strict requirements placed on the absorption properties of the resulting dye have to be provided, the options are relatively small.
Der Erfindung liegt die Aufgabe zugrunde, photographische Materialien durch Zusatz von Verbindungen zu verbessern, die an den belichteten Stellen durch Reaktion mit oxidiertem Entwickler entwicklungshemmende Substanzen abspalten, ohne dafl die aus dem Rest des ursprünglichen Moleküls bei der Reaktion mit dem Entwickleroxidationsprodukt entstehende Verbindung die photographischen Eigenschaften des Materials beeinflult;The invention is based on the object of improving photographic materials by adding compounds which split off development-inhibiting substances at the exposed areas by reaction with oxidized developer, without this the compound formed from the remainder of the original molecule in reaction with the developer oxidation product affects the photographic properties of the material;
Es wurde nun ein photographisches Material mit verbesserten photographischen Eigenschaften gefunden, das in mindestens einer lichtempfindlichen Silberhalogenidemulslansschicht oder einer benachbarten Schicht eine Verbindung enthält, die mit oxidiertem Entwickler unter Abspaltung von entwicklungshemmenden Substanzen reagiert, wobei die Reaktionsprodukte farblos sind oder im Laufe der photographischen VerarbeitungThere has now been found a photographic material with improved photographic properties, which in at least a light-sensitive silver halide emulsion layer or an adjacent layer contains a compound which is linked with oxidized developer reacts with the elimination of development-inhibiting substances, whereby the reaction products are colorless or in the course of photographic processing
A-G 238 - 3 - AG 238 - 3 -
909849/ 1 157909849/1 157
zu farblosen Substanzen umgesetzt werden, so dai3 diese Reaktionsprodukte nicht am Aufbau eines photographischen Farbbildes beteiligt sind.are converted to colorless substances, so that these Reaction products are not involved in the construction of a photographic color image.
Als bevorzugt geeignet haben sich Verbindungen der folgenden allgemeinen Formel erwiesen:Compounds of the following general formula have proven to be particularly suitable:
R
I R.
I.
X-C-S-EX-C-S-E
worin bedeuten:where mean:
£ = eine Gruppierung, die mit dem Schwefelatom der Thioätherbrücke als abgespaltene Mercaptoverbindung entwicklungs- hemmende Wirkung besitzt, z. B. heterocyclische Mercaptoverbindungen, wie Mercaptotetrazole, insbesondere Phenylmercaptotetrazole, Mercaptothiazole, Mercaptobenzthiazole, wie Mercaptoalkylamidothiazole oder -benzthiazole, Mercaptoazine, Mercaptoazole, Mercaptooxadiazole, Mercaptopyrimidin, Mercaptothiadiazole, Mercaptothiophen, Mercaptotriazin oder Mercaptotriazole, ferner Derivate von Thioglykolsäure, Mercaptocysteine, Mercaptoglutatione und ähnliche;£ = a grouping with the sulfur atom of the thioether bridge as a split-off mercapto compound has a development-inhibiting effect, e.g. B. heterocyclic mercapto compounds, such as mercaptotetrazoles, especially phenyl mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, such as mercaptoalkylamidothiazoles or -benzthiazoles, mercaptoazines, mercaptoazoles, mercaptooxadiazoles, mercaptopyrimidine, Mercaptothiadiazoles, mercaptothiophene, mercaptotriazine or mercaptotriazoles, also derivatives of thioglycolic acid, Mercaptocysteines, mercaptoglutate ions, and the like;
R = Wasserstoff, Alkyl mit vorzugsweise bis zu 18 C-Atomen, Aralkyl, wie Benzyl oder Phenyläthyl, Cycloalkyl, wie Cyclohexyl, Aryl, insbesondere Arylreste der Phenyl- oderR = hydrogen, alkyl with preferably up to 18 carbon atoms, Aralkyl, such as benzyl or phenylethyl, cycloalkyl, such as Cyclohexyl, aryl, especially aryl radicals of the phenyl or
A-G 238 - 4 - AG 238 - 4 -
, . . 909849/1157,. . 909849/1157
BÄDBATH
154764Ü154764Ü
Naphthylserle,, heterocyclische Reste mit 5 oder 6
Ringgliedern, wobei diese Ringe ein oder mehrere Heteroatome , wie N, 0, 3 oder Se und aneHierte Benzol- oder
Naphthalinringe enthalten können, wie z, B. Benzoxazol, Benzthiazol u» ä»
eine die Methylengruppe aktivierende Gruppierung wie Naphthylserle ,, heterocyclic radicals with 5 or 6 ring members, whereby these rings can contain one or more heteroatoms, such as N, 0, 3 or Se and aneHed benzene or naphthalene rings, such as, for example, benzoxazole, benzthiazole, etc.
a group activating the methylene group such as
G~lr, -G-H, -GOOH, -COOa1, -GON(E1 )2, -J-0 ύ G ~ l r , -GH, -GOOH, -COOa 1 , -GON (E 1 ) 2 , -J-0 ύ
CA ΪΙ ^qn ATS C! A W(T) Λ ,'M |CA ΪΙ ^ qn ATS C! A W (T) Λ, 'M |
oder die Gruppierung -S-Ejor the grouping -S-Ej
^"\~ {^gesättigte oder olefinisch ungesättigte aliphatisch« Reste mit bis zu 18 C-Atomen, vorzugsweise bis zu 5 C-Atomen, wobei diese Reste gegebenenfalls substituiert sein können mit z,B, Hydroxyl, Alkoxy, Halogen oder Arylresten, insbesondere Phenyl, wie Benzyl, Phenyläthyl oder Styryl,(2}Aryl vorzugsweise Phenyl oder Naphthyl, wobei die Phenylringe substituiert sein können oder (3)5-oder 6-gliedrige heterocyclische Heste,'die ein oder mehrere Heteroatome wie JJ, O, S oder Se oder anellierte Benzol- oder Naphthalinringe enthalten könnan» ^ "\ ~ {^ saturated or olefinically unsaturated aliphatic« radicals with up to 18 carbon atoms, preferably up to 5 carbon atoms, whereby these radicals can optionally be substituted with, for example , hydroxyl, alkoxy, halogen or aryl radicals, in particular Phenyl, such as benzyl, phenylethyl or styryl, (2} aryl, preferably phenyl or naphthyl, where the phenyl rings can be substituted or (3) 5- or 6-membered heterocyclic radicals, 'the one or more heteroatoms such as JJ, O, S or Se or fused benzene or naphthalene rings may contain »
--
Als besonders geeignet haben sich die folgenden Verbindungen erwiesen:The following compounds have proven to be particularly suitable:
A-G 238 - 5 - AG 238 - 5 -
909849/11St BAD OBlGlNAL909849 / 11St BAD OBlGlNAL
15478401547840
OH CO -OH CO -
-s-c^ (j-s-c ^ (j
^N- N ;ί^ N-N ; ί
Fp.ϊ 145~146°CMp 145 ~ 146 ° C
Ν— ΝΝ— Ν
C -C -
-S-C-S-C
N— NN-N
JS CJS C
IIIIII
■Ν— N■ Ν— N
Fp.: 115°CM.p .: 115 ° C
Fp, ϊ 134*137 CMp, 134 * 137 C
S CS C
N-N-
OHOH
CO-CH-Fp.: 115-1180CCO-CH-mp .: 115-118 0 C.
ff ν-« "'» ff ν- «"'»
11 III . 1— 1»11 III. 1— 1 »
-a 23B-a 23B
909849/ 1 157909849/1 157
IJH /UHUIJH / UHU
.C.C
IlIl
- CH - CH, Pp, 76-77°C - CH - CH, pp, 76-77 ° C
N NN N
N—N,N — N,
ν— rν— r
/ 2 5 / 2 5
C-S- CHn - C - NCS-CH n -C-N
Il ■ \Il ■ \
O C2H5O C 2 H 5
Fp.: 7^-75 CM.p .: 7 ^ -75 C
N— VH IlN— VH Il
C-S-CH-C-N C2H5 CS-CH-CN C 2 H 5
N— NN-N
Il >Il>
N— N^N - N ^
S OS O
C2H5 C 2 H 5
Fp.: 111-113 CM.p .: 111-113 C
VIIIVIII
Ν— ΝΝ— Ν
S-C.S-C.
- CH- CH
Ν— ΝΝ— Ν
,N— N, N-N
S-CS-C
— N Fp.: 97-lo2uC - N mp .: 97 lo2 u C
A-G 238A-G 238
-7- 9 0 9849/1157-7- 9 0 9849/1157
C-CH^-S-CC-CH ^ -S-C
Ν— ΝΝ— Ν
IlIl
Ν— NΝ— N
öloil
X (CH3J2HCX (CH 3 J 2 HC
CH(CH,),CH (CH,),
C-CH2-S-C^C-CH 2 -SC ^
CH(CH3),, N— CH (CH 3 ) ,, N—
Fp;1131-133 CM.p .; 1131-133 C
CO-CH^-S-CCO-CH ^ -S-C
N— NN-N
N NN N
Fp.ί 119-12o°CMp 119-12o ° C
CHCH
COCO
CH2 - SCH 2 - S
CHCH
Fp.: l6o-l62°CM.p .: 160-162 ° C
A-G 238A-G 238
909849/1909849/1
XIIIXIII
N— NN-N
%-CO - % -CO -
CH2-SCH 2 -S
Fp.; 188-19o°CM.p .; 188-19o ° C
N— NN-N
Ν— ΝΝ— Ν
// \s— CO - CH2 - S - C // \ s - CO - CH 2 - S - C
Il Fp-! Il Fp - !
— N- N
/ W-CO-NH N—N / W-CO-NH N-N
SO2F J/ V-CO-CH2-S-CSO 2 F J / V-CO-CH 2 -SC
— N- N
Il Fp.: 138-142° II m.p .: 138-142 °
Η,ΟΗ, Ο
C-CH2 - Pp.; 11.2-1 C-CH 2 - pp; 11.2-1
ί-G 909-8 49/ It SI ί-G 909-8 49 / It SI
XVII CH^-C-CH9-S-CT ||XVII CH ^ -C-CH 9 -S-CT ||
6H5 Pp.; 76-780C 6 H 5 pp .; 76-78 0 C
OOHOOH
cccc
S-CH0-CS-CH 0 -C
Il O Pp.: 136-138 C II O pp: 136-138 C
COOHCOOH
N NN N
WHWH
Pp.: 12O0CPp .: 12O 0 C
XXII NaO3SXXII NaO 3 S
Fp.i s 300 CM.p.s 300 ° C
- ro- ro US/ %% US / %%
XXIII HaOXXIII HaO
XXIVXXIV
ClO2SClO 2 S
Il Fp.: 105°C Ti—NII m.p .: 105 ° C Ti-N
N C-S-CHo-C0_/~\-CN CS-CH o -C0_ / ~ \ -C
CSCH0 IlCSCH 0 Il
Öloil
XXVI " 1<£^>i^S\ XXVI " 1 <£ ^> i ^ S \
12H25 Ö1 12 H 25 Ö1
XXVIIXXVII
Ν—it Ν— it
. Fp.: 93-94 C. M.p .: 93-94 C
A-G 238A-G 238
-- 909849/1157909849/1157
1 5476A01 5476A0
XXVIIIXXVIII
O2PO 2 P
^NN CO-CH9-S-C |l^ NN CO-CH 9 -SC | l
d NN-N d N NN
Pp.: 59-6O0CPp: 59-6O 0 C
V-SO9-CHV-SO 9 -CH
N—NN-N
C-CH9-SC-CH 9 -S
IlIl
0-NH-C18H37 O-NH-C 18 H 37
H N-NH N-N
O-C-S-/ IlO-C-S- / II
it L ii-Nit L ii-N
NHGN INH GN I
Im folgenden ist die Herstellung von in der erfindungsgemäßen Weise zu verwendenden Verbindungen beschrieben!The following is the preparation of in the invention Way to use connections described!
A-G 238A-G 238
- 12 -- 12 -
909849/ 1909849/1
Verbindung I Compound I.
20 g 2-'-'hloracet;/l~i—krejol und20 g of 2 -'- 'chloroacet; / l ~ i-krejol and
21,8 g N-Phenyl-mercapto-tetrazol-natriuin werden in 25Occm Aceton 15 Minuten lang unter Rückiluü erhitzt.21.8 g of N-phenyl-mercapto-tetrazole-natriuin are heated in 25Occm acetone for 15 minutes under Rückiluü.
Das ausfallende Natriumchlorid wird heiß abgesaugt und das FiI-trat eingeengt. Das auskristallisierte Reaktion3produkt wird aus Aceton umkristallisiert.The sodium chloride which precipitates out is filtered off with suction while hot and the filtrate is removed constricted. The crystallized reaction product turns out Recrystallized acetone.
Ausbeute: fast quantitativ Fp.: 145-146 GYield: almost quantitative m.p .: 145-146 g
Die Verbindungen II bis VIII werden in ähnlicher tfeise Hergestellt. The compounds II to VIII are prepared in a similar manner.
Verbindung II kann sowohl :ius u-Chloracetophenon und dem Natriumsalz des N-Fhenyl-mercaptotetrazols als auch aus Acetophenon und dem Sulfenylehlorid des N-Phenyl-mercaptotetrazols dargestellt· werden.Compound II can be both: ius u-chloroacetophenone and dem Sodium salt of N-fhenyl-mercaptotetrazole as well Acetophenone and the sulfenyl chloride of N-phenyl-mercaptotetrazole being represented.
p-Isododecyl- lu-chlor-acetophenonp-Isododecyl-lu-chloro-acetophenone
In eine Lösung von 186 g Isododecylbenzol, 100 g Chloracetylchlorid und 300 ecm üchwefelKohlenstoff trägt man innerhalb von 30 Minuten 10,5 g feingepulvertes Aluminiumchloride Anschließend erhitzt man 2 Stunden lang auf dem Wasserbad, destlliert den Schwefelkohlenstoff ab und zersetzt den Rückstand mitIn a solution of 186 g of isododecylbenzene, 100 g of chloroacetyl chloride and 300 ecm of carbon sulfur is carried inside 10.5 g of finely powdered aluminum chloride after 30 minutes heated for 2 hours on a water bath, distilled the carbon disulfide and decomposes the residue with
A-S 238 - 13 -A-S 238 - 13 -
909849/ 1 157909849/1 157
βι'.'Ο g ^io, iO'j ι:.! Wasser und oO ecm konz. salzsäure. Das
Reaktionär nviuKt wird in Ätner y.jigenojrjnen, ier ätherische
Extrakt mit wäcri^yr oodai^surig ge3ci-.att.elt ini tr.aehlie^
mit Wasser neutral. gewa.K'her:. Der Äther wird n-icr. lern Troe «er-η
abdestiiliert ind ier Rückstand im Hocnvaicuum ieatilliert.
Kp. 0,6 ram ca. ab 17U0C
Ausbeute: 160-JOO gβι '.' Ο g ^ io, iO'j ι:.! Water and oO ecm conc. hydrochloric acid. The reactionary nviuKt is y.jigenojrjnen in Ätner, ier ethereal extract with wäcri ^ yr ^ oodai surig ge3ci-.att.elt ini tr.aehlie ^ neutral with water. gewa.K'her :. The ether becomes n-icr. Learn troubles are distilled off and the residue is distilled in a vacuum. Kp. 0.6 ram approx. From 17U 0 C
Yield: 160-JOO g
160 g p-Iaododecyl-vu-chlor-acetophenol und * 1u0 g N-thenyl-mercapto-tetrazol-natrium werden 30 Minuten lang in 500 ml abs. Aceton unter Rückfluß erhitzt. Das ausfallende Natriumchlorid wird ?iog^rfa?igt um las PiLtrat bis zu einem viakoäen 1 eingeengt. Ausbeute: ca. c:l·. -) g160 g of p-Iaododecyl-vu-chloro-acetophenol and * 1u0 g of N-thenyl-mercapto-tetrazole sodium are dissolved in 500 ml of abs for 30 minutes. Acetone heated to reflux. The sodium chloride which precipitates out is concentrated in the form of the filtrate to a concentration of 1. Yield: approx. C: l ·. -) g
Un: d as Reakti.>nst:ro"iukt v;n evtl. opuren '/on I.'-i her.vioieroaptotetrazoi zu Defreien, nimmt man es in Jnlorcform auf und erwärmt diese Losung Kurze Zeit mit etwas oilberr;.- mid. Anschließend wird filtriert and wieder eingeengt.Un: T he Reakti> nst. Ro "ICT play v n possibly opuren '/ on I .'- i her.vioieroaptotetrazoi to Defreien takes ma n it in Jnlorcform and heats this solution oilberr short time with some ;. - mid. It is then filtered and concentrated again.
Die '/erbindungen X ois XII werden in ähnlicher «eise lar.-restellt. ■The '/ erbindungen X and XII are in a similar way. ■
A-G 238 - 14 - AG 238 - 14 -
909849/1157909849/1157
BADBATH
Verbindung XIY Methode A
p-Lauroy1-amiηο-acetophenon Connection XIY method A
p-Lauroy1-amiηο- acetophenone
27 g (0,2 Mol) + 4-Amino-acetophenon werden in 150 ml Pyridin gelöst und bei Zimmertemperatur unter Kühren langsam 45,6 g (0,2 Mol) Laurin3äurechlorid zugetropft. Ks Aird 2 Stunden lang nachgerührt, eine weitere «Stunde lang auf 50-6O0C erwttrmt und schließlich auf üis und konz. Salzsäure ausgetragen. Der Niederschlag wird abgesaugt und aus Methanol umkristallisiert. Pp.: 1O4-1O5°C27 g (0.2 mol) of + 4-aminoacetophenone are dissolved in 150 ml of pyridine and 45.6 g (0.2 mol) of lauric acid chloride are slowly added dropwise at room temperature while stirring. Ks Aird 2 hours stirring, erwttrmt another "hour at 50-6O 0 C and finally concentrated on and üis. Hydrochloric acid discharged. The precipitate is filtered off with suction and recrystallized from methanol. Pp .: 104-1O5 ° C
In eine Losung von 15f8 g p-Lauroyl-amino-acetophenon in abs.
Tetrachlorkohlenstoff fugt man eine Lösung von 1υ,8 g
1-Phenyl-5-tetrazoloyl-sulfenylchlorid in aus. Tetrachlorkohlenstoff.
Man läßt die Mischung über Nacht stehen, saugt den ausgefallenen Niederschlag ab und kristallisiert aus
Methanol um.
Pp.: 138-142°CIn a solution of 15 f 8 g of p-lauroyl-amino-acetophenone in abs. Carbon tetrachloride is added to a solution of 1½.8 g of 1-phenyl-5-tetrazoloyl-sulfenyl chloride. Carbon tetrachloride. The mixture is left to stand overnight, the precipitate which has separated out is filtered off with suction and recrystallized from methanol.
P.p .: 138-142 ° C
Methode BMethod B.
Dieselbe Verbindung ist ebenfalls gut darstellbar aus Verbindung XIII und Laurinsäurechlorid. Schmelzpunkte und IR-Spektren sind identisch.The same connection can also be represented well from connection XIII and lauric acid chloride. Melting points and IR spectra are identical.
Die erfindungsgemäßen photographischen Materialien sind sowohl für die Herstellung von schwarz-weißen als auch - und dies bevorzugt - für die Herstellung von Farbbildern geeignet.The photographic materials according to the invention are for the production of black and white as well as - and this preferred - suitable for the production of color images.
A-G 238 - 15 - AG 238 - 15 -
909849/1157909849/1157
ORiGiNALOriginal
Die den entwicklungshemmenden Rest enthaltenden Zusätze können dabei in der verschiedensten Form dem photographischen Material zugesetzt werden. Sie können in diffusionsfester oder nicht diffusionsfester Form, in gelöster oder einemulgierter Form angewendet werden. Die jeweils günstigste Anwendungsform hängt von dem Verwendungszweck ab und kann durch einfache Versuche ermittelt werden.The additives containing the development-inhibiting residue can be used in the most varied of forms in the photographic Material can be added. They can be in diffusion-proof or non-diffusion-proof form, in dissolved or emulsified form Shape to be applied. The most favorable form of application in each case depends on the intended use and can go through simple experiments can be determined.
Als lichtempfindliche Schichten sind die üblichen Halogensilberschichten geeignet, wobei die lichtempfindlichen Silberhalogenide in den üblichen hydrophilen Bindemitteln, vorzugsweise Gelatine, dispergiert sind.The usual halogen silver layers are used as light-sensitive layers suitable, the light-sensitive silver halides in the usual hydrophilic binders, preferably Gelatin, are dispersed.
Die lichtempfindlichen Schichten enthalten vorzugsweise die üblichen Farbkuppler, die mit den üxidationsprodukten farbgebender Entwickler zu Farbstoffen kuppeln. Die lichtempfindlichen Schichten können ferner in üblicherweise optisch oder chemisch sensibilisiert sein bzw. die üblichen Stabilisatoren und sonstigen Zusätze enthalten.The light-sensitive layers preferably contain the customary color couplers, which give color to the oxidation products Coupling developers to form dyes. The photosensitive layers can also be conventionally optical or be chemically sensitized or contain the usual stabilizers and other additives.
Für die Entwicklung der belichteten, erfindungsgemäßen Materialien sind Entwicklergemische üblicher Zusammensetzung mit Entwicklersubstanzen, die mindestens eine primäre aromatische Aminogruppe enthalten, geeignet, z. B.:Developer mixtures of customary composition are used for developing the exposed materials according to the invention with developer substances which contain at least one primary aromatic amino group, suitable, for. B .:
A-S 238 - 16 - AS 238 - 16 -
909849/1157909849/1157
Ν,Ν-Diäthyl-p-phenylendiamin;
N-Äthyl-N-vo-aulfobutyl-p-phenylendiamin;
2-Amino-5-diäthylaminotoluol;
p-Amino-N-äthyl-N-ß-hydroxyäthylanilin.Ν, Ν-diethyl-p-phenylenediamine;
N-ethyl-N-vo-aulfobutyl-p-phenylenediamine; 2-amino-5-diethylaminotoluene;
p-Amino-N-ethyl-N-ß-hydroxyethylaniline.
Schicht I: ,Layer I:,
1 g der Verbindung I wird in 1 ecm DiDutylphthalat und 6 ecm Essigester gelöst und in 40 ecm 7,5 ^iger Gelatine unter Zugabe von 2 ecm einer 2 #igen Lösung von Dodecylbenzolsulfonat emulgiert. Das Emulgat wird mit 40 ecm einer lichtempfindlichen Silberbromidjodidgelatineemulsion (5 Mol-# kg) gemischt und auf einen Schichtträger aus Celluloseacetat vergossen. Schichtdicke: 5/U.1 g of compound I is dissolved in 1 ecm of di-butyl phthalate and 6 ecm of ethyl acetate and emulsified in 40 ecm of 7.5% gelatin with the addition of 2 ecm of a 2% solution of dodecylbenzenesulfonate. The emulsification is mixed with 40 ecm of a light-sensitive silver bromide iodide gelatin emulsion (5 mol- # kg) and poured onto a layer support made of cellulose acetate. Layer thickness: 5 / U.
Schicht II:Layer II:
Zum Vergleich werden 1 ecm Dibutylphthalat, 6 ecm Eaaigester und 4o ecm 7*5#ige Gelatine emulgiert, das Emulgat mit 4o ecm der gleichen lichtempfindlichen Silberhalogenidemulsion gemischt und wie oben auf einen Träger vergossen.For comparison, 1 ecm dibutyl phthalate, 6 ecm Eaigester and 4o ecm 7 * 5 # gelatine emulsified, the emulsified with 4o ecm the same light-sensitive silver halide emulsion and poured onto a carrier as above.
Beide Schichten werden wie folgt verarbeitet.:Both layers are processed as follows:
a) Man belichtet hinter einem Stufenkeil und entwickelt anschlielend 8 Minuten bei 2o°C in einem Farbentwickler folgender Zusammensetzung:a) One exposes behind a step wedge and then develops 8 minutes at 20 ° C in a color developer with the following composition:
A-G^23B -- 17 -AG ^ 23B - 17 -
9 0 9 8 4 9/11579 0 9 8 4 9/1157
BAD ORiOiNALBAD ORiOiNAL
Ν,Ν-Diäthyl-p-phenylendiaminsulfat 2,5 g Natrium3ulfit aicc. 2,0 gΝ, Ν-diethyl p-phenylenediamine sulfate 2.5 g Sodium sulfite aicc. 2.0 g
Kaliumbromid 1 ,0 gPotassium bromide 1.0 g
Kaliumcarbonat sice. 75,0 gPotassium carbonate sice. 75.0 g
p-Nitrobenzylcyanid ala Purpurkuppler 0,7 g Waaser 1 1p-nitrobenzyl cyanide ala purple coupler 0.7 g Waaser 1 1
Die Proben werden nach der üblichen Zwischenwässerung in einer " lo^igen Kaliuraferricyanldlösung gebleicht und anschließend in einer Natriumthiosulfatlösung fixiert. Man erhält ein Purpurfarbstoffbild, dessen empfindlichkeit in beiden Fällen die gleiche ist. Der f -Wert der Schicht II (ohne Zusatz beträgt o,95; der/'-Wert der Schicht I (mit Zusatz) ist Jedoch auf o,4 gedrückt.After the usual intermediate rinsing, the samples are bleached in a 10% potassium ferricyanide solution and then fixed in a sodium thiosulphate solution. A purple dye image is obtained, the sensitivity of which is the same in both cases. The f value of layer II (without addition is 0.95 ; The / 'value of layer I (with addition) is, however, pressed down to 0.4.
Man entwickelt die Schichten I und II in einem Entwickler folgender Zusammensetzung: One develops the layers I and II in a developer of the following composition:
( p-Methylaminophenol o,7 β ( p-methylaminophenol o, 7 β
Hydrochinon 2,5 gHydroquinone 2.5 g
Natriumsulfit sicc. lo,o gSodium sulfite sicc. lo, o g
Natriumcarbonat sicc. 25,ο gSodium carbonate sicc. 25, ο g
Kaliumbromid l,o gPotassium bromide l, o g
-g 238 - 18 - -g 238 - 18 -
909849/1909849/1
BAD ORIGINALBATH ORIGINAL
und fixiert in einer 20 $igen Natriumthio3ulfatlösung. In diesem Falle findet keine Einwirkung auf die Entwicklung statt. Gradation und Empfindlichkeit beider Schichten sind identisch.and fixed in a 20% sodium thio3ulfate solution. In in this case there is no influence on the development. Gradation and sensitivity of both layers are identical.
Beispiel 2
Schicht I: Example 2
Layer I:
6,5 g der Verbindung IX werden in J5o ecm Essigester und 7 g Dibutylphthalat gelöst und in 15o ecm lediger Gelatine emulgiert. 13o ecm des Emulgats werden mit 1 kg einer lichtempfindlichen Silberbromidgelatineeinulsion vermischt. Diese Mischung wird mit 4oo ecm einer 4#igen Lösung eines Kupplers l-Hydroxy-2-naphtoesäure-/"2-(N-methyl-N-octadecylamino)-5-sulfosäure^7anilid versetzt und auf einen Träger vergossen.6.5 g of the compound IX are dissolved in 150 ml of ethyl acetate and 7 g Dissolved dibutyl phthalate and emulsified in 15o ecm single gelatin. 13o ecm of the emulsifier are mixed with 1 kg of a light-sensitive Silver bromide gelatin emulsion mixed. This mixture is mixed with 4oo ecm of a 4 # solution of a coupler l-hydroxy-2-naphthoic acid - / "2- (N-methyl-N-octadecylamino) -5-sulfonic acid ^ 7anilide offset and potted on a carrier.
Schicht II:Layer II:
Eine Vergleichsschicht II wird unter den gleichen Bedingungen mit dem Farbkuppler allein hergestellt. Die Schichtdicke stellt man so ein, daß bei der Schwarz-Weifi-Entwicklung nach Beispiel 1 b) die Schicht I zu einem Gamma von o,8 entwickelt wird, die Schicht II jedoch nur zu einem Gammawart von 0,5.A comparison layer II is made under the same conditions made with the color coupler alone. The layer thickness is adjusted so that in the black-and-white development according to Example 1 b) layer I is developed to a gamma of 0.8, but layer II is only developed to a gamma of 0.5.
A-G 238 - 19 - AG 238 - 19 -
909-849/1157909-849 / 1157
SAD ORIGINALSAD ORIGINAL
Dae belichtete Material wurde in einen Farbentwickler folgender Zusammensetzung entwickelt:The exposed material was used in a color developer as follows Composition developed:
4-Amino-N,N-diäthylanilinsulfat 2,5 g4-Amino-N, N-diethylaniline sulfate 2.5 g
Wasser 1 1Water 1 1
Man erhält ein blaugrüneβ Farbstoffbild. Trotz des unter-W schiedlichen Silberauftrages erhält man in beiden Fällen die gleiche Empfindlichkeit und die gleiche Oradation. Das Farbbild der Schicht I zeigt ein feineres Korn.A blue-green dye image is obtained. Despite the lower silver W difference union order to obtain the same sensitivity and the same Oradation in both cases. The color image of layer I shows a finer grain.
A-G 238 - 20 - AG 238 - 20 -
909849/1117909849/1117
BAD ORIGINALBATH ORIGINAL
Claims (4)
X ■ eine die Methylengruppe aktivierende Gruppierung.and may contain fused benzene or naphthalene rings;
X ■ a group which activates the methylene group.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA0055408 | 1967-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1547640A1 true DE1547640A1 (en) | 1969-12-04 |
Family
ID=6939983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19671547640 Pending DE1547640A1 (en) | 1967-04-10 | 1967-04-10 | Improved Photographic Material |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3632345A (en) |
| BE (1) | BE713448A (en) |
| CH (1) | CH506095A (en) |
| DE (1) | DE1547640A1 (en) |
| FR (1) | FR1568390A (en) |
| GB (1) | GB1224555A (en) |
| NL (1) | NL6805089A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2359295A1 (en) * | 1972-11-29 | 1974-05-30 | Konishiroku Photo Ind | DEVELOPMENT INHIBITORS RELEASE COMPOUNDS, DEVELOPMENT METHODS WORKING USING SUCH COMPOUNDS FOR LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS AND THESE COMPOUNDS PHOTOGRAPHIC RECORDS CONTAINED |
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|---|---|---|---|---|
| FR2119523A5 (en) * | 1970-12-22 | 1972-08-04 | Eastman Kodak Co | |
| US4202695A (en) * | 1971-12-09 | 1980-05-13 | Agfa-Gevaert N.V. | Photographic Lippmann emulsions |
| JPS5116142B2 (en) * | 1972-12-18 | 1976-05-21 | ||
| JPS5119987B2 (en) * | 1973-02-05 | 1976-06-22 | ||
| US4009029A (en) * | 1973-06-05 | 1977-02-22 | Eastman Kodak Company | Cyanoethyl-containing blocked development restrainers |
| JPS5939738B2 (en) * | 1973-08-16 | 1984-09-26 | コニカ株式会社 | Multilayer color photographic material |
| JPS50152731A (en) * | 1974-05-29 | 1975-12-09 | ||
| JPS516724A (en) * | 1974-07-06 | 1976-01-20 | Konishiroku Photo Ind | Harogenkaginshashinkankozairyo |
| DE2502892A1 (en) * | 1975-01-24 | 1976-07-29 | Agfa Gevaert Ag | LIGHT SENSITIVE COLOR PHOTOGRAPHIC MATERIAL |
| JPS5223344A (en) * | 1975-08-15 | 1977-02-22 | Konishiroku Photo Ind Co Ltd | Silver halide photographic light sensitive material |
| JPS537232A (en) * | 1976-07-07 | 1978-01-23 | Fuji Photo Film Co Ltd | Silver halide photographic photosensitive material |
| JPS5370821A (en) * | 1976-12-07 | 1978-06-23 | Fuji Photo Film Co Ltd | Silver halide photographic material |
| DE2704797C2 (en) * | 1977-02-05 | 1982-05-27 | Agfa-Gevaert Ag, 5090 Leverkusen | Color photographic recording material |
| DE2707489C2 (en) * | 1977-02-21 | 1983-10-06 | Agfa-Gevaert Ag, 5090 Leverkusen | Color photographic recording material |
| US4226934A (en) * | 1977-08-12 | 1980-10-07 | Ciba-Geigy Ag | Light sensitive photographic material containing development inhibitor releasing compounds |
| JPS54118245A (en) * | 1978-01-26 | 1979-09-13 | Ciba Geigy Ag | Color photographic material |
| JPS56116029A (en) * | 1980-01-16 | 1981-09-11 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| JPS56114946A (en) * | 1980-02-15 | 1981-09-09 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| US4343893A (en) * | 1980-07-25 | 1982-08-10 | E. I. Du Pont De Nemours And Company | Masked development/image modifier compounds of silver photographic systems |
| US4593108A (en) * | 1981-01-05 | 1986-06-03 | Polaroid Corporation | 1-phenyl-5-mercapto tetrazoles |
| US4350754A (en) * | 1981-06-12 | 1982-09-21 | Polaroid Corporation | Blocked development restrainers |
| US4461826A (en) * | 1981-07-10 | 1984-07-24 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive color photographic material |
| JPS58154842A (en) * | 1982-02-03 | 1983-09-14 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| AU568488B2 (en) | 1982-02-24 | 1988-01-07 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide colour photographic material |
| JPS58217932A (en) * | 1982-06-11 | 1983-12-19 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material |
| JPS59116647A (en) | 1982-12-13 | 1984-07-05 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS59188641A (en) | 1983-04-11 | 1984-10-26 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
| JPS60143331A (en) | 1983-12-29 | 1985-07-29 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| US4725529A (en) * | 1985-04-30 | 1988-02-16 | Konishiroku Photo Industry Co., Ltd. | Developing inhibitor arrangment in light-sensitive silver halide color photographic materials |
| JPS61255342A (en) | 1985-05-09 | 1986-11-13 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| DE3682128D1 (en) | 1985-07-17 | 1991-11-28 | Konishiroku Photo Ind | PHOTOGRAPHIC SILVER HALOGENID MATERIAL. |
| JPH0711695B2 (en) | 1985-09-25 | 1995-02-08 | 富士写真フイルム株式会社 | Processing method of silver halide color light-sensitive material for photography |
| AU591540B2 (en) | 1985-12-28 | 1989-12-07 | Konishiroku Photo Industry Co., Ltd. | Method of processing light-sensitive silver halide color photographic material |
| US4855220A (en) * | 1988-01-14 | 1989-08-08 | Eastman Kodak Company | Photographic element having layer for increasing image sharpness comprising a non-diffusible DIR compound |
| EP0574090A1 (en) | 1992-06-12 | 1993-12-15 | Eastman Kodak Company | One equivalent couplers and low pKa release dyes |
| DE4310327A1 (en) * | 1993-03-30 | 1994-10-06 | Du Pont Deutschland | Method of producing negative images with ultra-contrast contrast |
| JP3240342B2 (en) * | 1994-06-09 | 2001-12-17 | コニカ株式会社 | Silver halide color photographic materials |
| US5681691A (en) | 1995-12-11 | 1997-10-28 | Eastman Kodak Company | Photographic element containing an improved pyrazolotriazole coupler |
| US5985532A (en) | 1995-12-11 | 1999-11-16 | Eastman Kodak Company | Photographic element containing an improved pyrozolotriazole coupler |
| EP0921435B1 (en) * | 1997-12-02 | 2002-07-24 | Tulalip Consultoria Comercial Sociedade Unipessoal S.A. | Light-sensitive silver halide photographic elements containing yellow filter dyes |
| US7271195B2 (en) * | 2003-06-10 | 2007-09-18 | Kalypsys, Inc. | Carbonyl compounds as inhibitors of histone deacetylase for the treatment of disease |
| EP1921073A1 (en) * | 2006-11-10 | 2008-05-14 | Laboratorios del Dr. Esteve S.A. | 1,2,4-Triazole derivatives as sigma receptor inhibitors |
| US8555875B2 (en) * | 2008-12-23 | 2013-10-15 | Map Pharmaceuticals, Inc. | Inhalation devices and related methods for administration of sedative hypnotic compounds |
| US20130052594A1 (en) | 2011-08-31 | 2013-02-28 | Diane M. Carroll-Yacoby | Motion picture films to provide archival images |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3148062A (en) * | 1959-04-06 | 1964-09-08 | Eastman Kodak Co | Photographic elements and processes using splittable couplers |
| BE589419A (en) * | 1959-04-06 | |||
| US3459549A (en) * | 1967-07-13 | 1969-08-05 | Eastman Kodak Co | Bridged dihydroxynaphthalene and bridged dihydroxyanthracene silver halide developing agents and antifoggants |
-
1967
- 1967-04-10 DE DE19671547640 patent/DE1547640A1/en active Pending
-
1968
- 1968-04-02 US US723344A patent/US3632345A/en not_active Expired - Lifetime
- 1968-04-03 GB GB05980/68A patent/GB1224555A/en not_active Expired
- 1968-04-08 CH CH526168A patent/CH506095A/en not_active IP Right Cessation
- 1968-04-10 NL NL6805089A patent/NL6805089A/xx unknown
- 1968-04-10 BE BE713448A patent/BE713448A/xx unknown
- 1968-04-10 FR FR1568390D patent/FR1568390A/fr not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2359295A1 (en) * | 1972-11-29 | 1974-05-30 | Konishiroku Photo Ind | DEVELOPMENT INHIBITORS RELEASE COMPOUNDS, DEVELOPMENT METHODS WORKING USING SUCH COMPOUNDS FOR LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS AND THESE COMPOUNDS PHOTOGRAPHIC RECORDS CONTAINED |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1224555A (en) | 1971-03-10 |
| US3632345A (en) | 1972-01-04 |
| FR1568390A (en) | 1969-05-23 |
| CH506095A (en) | 1971-04-15 |
| BE713448A (en) | 1968-08-16 |
| NL6805089A (en) | 1968-09-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E771 | Valid patent as to the heymanns-index 1977, willingness to grant licences |