EP0083354B1 - Anionische oberflächenaktive verbindungen, photographische elemente die diese verbindungen enthalten und verfahren zur herstellung der elemente - Google Patents

Anionische oberflächenaktive verbindungen, photographische elemente die diese verbindungen enthalten und verfahren zur herstellung der elemente Download PDF

Info

Publication number
EP0083354B1
EP0083354B1 EP82902078A EP82902078A EP0083354B1 EP 0083354 B1 EP0083354 B1 EP 0083354B1 EP 82902078 A EP82902078 A EP 82902078A EP 82902078 A EP82902078 A EP 82902078A EP 0083354 B1 EP0083354 B1 EP 0083354B1
Authority
EP
European Patent Office
Prior art keywords
group
compound
coating
surface active
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82902078A
Other languages
English (en)
French (fr)
Other versions
EP0083354A1 (de
Inventor
John Frank Padday
Allan Robert Pitt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0083354A1 publication Critical patent/EP0083354A1/de
Application granted granted Critical
Publication of EP0083354B1 publication Critical patent/EP0083354B1/de
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • G03C1/385—Dispersants; Agents facilitating spreading containing fluorine

Definitions

  • the present invention relates to anionic compounds comprising fluorocarbons and polyglycidyl groups. These compounds are particularly useful surface active agents and can be used as coating aids in coating photographic elements.
  • the invention further relates to photographic elements containing such anionic compounds and to processes for preparing such elements.
  • a support is often coated with one or more layers comprising an aqueous solution of gelatin or other hydrophilic binder.
  • layers are generally coated simultaneously on conventional photographic supports as described in US ⁇ A ⁇ 2,761,791.
  • a critical commercial step in preparing photographic elements is the coating of a photographic emulsion (a dispersion of silver halide crystals in an aqueous binder) onto the support.
  • the coating process is generally carried out on a continuously operating machine wherein a single layer or a plurality of layers are simultaneously applied to the support.
  • the coating compositions used lie on the surface of the support so as to form a distinct layer of uniform thickness.
  • the layers once formed should be stable to deformation from spreading, chilling, drying or other common coating treatments.
  • a wide variety of surface active agents such as alkyl aryl polyether sulphonates, have been suggested for use as coating aids to control and enhance coating uniformity, to reduce certain types of layer thickness non-uniformities and to impart certain physical properties to the surface of the coated product.
  • Surfactants are also added to eliminate coating problems such as formation of cross-roll patterns due to poor static or dynamic wettability of the support. Other problems involve edge withdrawal and layer inversion in simultaneous multilayer applications, repellency spots and poor wetting of the coating application apparatus.
  • a surfactant which controls the surface properties of the coating and additionally has the proper solubility characteristics to avoid the above problems is much sought after.
  • the surfactants generally should reduce the surface tension of aqueous solutions to low values, contribute to favourable wettability properties of the uppermost surface of the dried product, and be effective in allowing the manufacture of uniform coatings which are free of repellency spots.
  • non-ionic compounds containing fluorinated hydrocarbon and polyglycidyl groups as described in British Specification 1,524,631. Unfortunately such nonionic compounds provide highly variable results when they are used as coating aids as illustrated in Example 3 below.
  • FR-A-2,260,812 discloses the addition of an organic fluoro compound to the surface layer of a photographic light-sensitive material as a means of improving its adhesion resistance.
  • the present invention provides a novel class of fluorocarbon surfactants which because of the presence of an anionic group, allow the surfactants to be water-soluble while keeping the molecule size to a minimum.
  • fluorocarbon surfactants performing excellently in photographic coating compositions in general it is believed that those of relatively small molecular size will be especially useful in high speed coating applications where the dynamic rheological properties become increasingly significant.
  • a water-soluble surface active compound consisting of a terminal fluorocarbon group linked by a linking group to a polyglycidyl chain comprising a random mixture of groups of the formula having attached thereto at least one anion, the or each anion having an associated cation.
  • the present surfactants provide desirable surface properties to coatings resulting in coated products which are uniform and free of adverse photographic and sensitometric problems.
  • the anion is sulphate.
  • the polyglycidyl group may be linked to the fluorocarbon group by a hydrocarbon group, e.g. CH 2 .
  • a preferred class of surfactants according to this invention have the formula: wherein Y is a fluorocarbon group;
  • the preferred linking group X has the formula: wherein Z is an ether, ester, amine, amido or sulphonamido linking group; and D is an ether or amine linking group; c is 0 or 1; m is 0 or 1; and b is 0 or 1 provided that where b is 0, c+m is 1 and when b is 1, m is 0 and c is 0 or 1.
  • Examples of groups which Z and D may represent are -0-, -O-CO-, -CO-O-, -NR-, -CONH-, -NHCO, -S0 2 NH- and -NH-SO 2 - wherein R is alkyl or aryl.
  • linking groups X are alkylene preferably containing from 1 to 6 carbon atoms such as methylene, isopropylene; or arylene such as phenylene.
  • the preferred linking group is CH 2 .
  • Polyglycidyl groups are well-known and described, for example, in US-A-3,514,293. These groups are optionally named poly(hydroxypropylene ethers) and have the formula C 3 H 6 O 2 . They are believed to comprise a random mixture of groups of the formula
  • the polyglycidyl chains are formed in known manner by condensing glycidol to form a linear or branched chain linked by ether bonds.
  • T 1 and T 2 are each independently anionic groups attached to E. They preferably comprise anions derived from an organic or inorganic acid.
  • anionic groups represented by T 1 include sulphosuccinate, sulphonate, sulphate and phosphate.
  • the anionic group T 2 links together two or more (YXET) units.
  • two such units may be attached to either of the following anionic groups: to form the appropriate double ester.
  • the surfactant of the invention contains more than one anionic group it is possible for them to comprise more than one type of anionic group.
  • the maximum number of anionic groups present may equal the number of sites in E to which the anionic group are attachable.
  • Examples of monovalent cations M are Li + , Na + , K + and NR' 4 wherein each R' independently represents hydrogen or alkyl, preferably containing 1 to 3 carbon atoms such as methyl and propyl.
  • a preferred class of surfactants have the formula: wherein T 1 is an anionic group, M is a cationic group, A is H or F and f is from 4 to 8, preferably 6 to 8 and d is from 2 to 30, often 4 to 30 and preferably 2 to 10.
  • the fluorosurfactants of the present invention are useful alone or in combination with conventional anionic and non-ionic surfactants to achieve improved surface properties.
  • the number of polyglycidyl groups (d) represents an average value with a distribution of molecular weight around this value.
  • the surface active agents of the present invention are prepared by methods in themselves known from a suitable fluorocarbon starting material.
  • Suitable fluorocarbon starting compounds have a labile functional group or atom such as iodide or a carboxylic acid, sulphonic acid, amine, alcohol or ethylenically unsaturated group.
  • the fluorocarbon is reacted with a bifunctional hydrocarbon compound in which the functional groups are both hydroxyl groups such as ethylene glycol; both amine groups such as ethylenediamine; or containing one hydroxyl group and one amino group such as ethanolamine.
  • the functional group of the fluorocarbon starting compound may be a carboxylic acid chloride to yield the amide or ester link, or sulphonyl chloride to yield the sulphonamide link.
  • Linking group D is formed by reaction of the remaining free functional group of the hydrocarbon with glycidyl.
  • the anionic groups are attached to the polyglycidol chain by conventional techniques such as sulphation and phosphation.
  • the cation is added by neutralizing to the salt.
  • the invention also provides a photographic element comprising a support having thereon at least one layer containing a hydrophilic colloid and a surfactant characterised in that the surfactant is one according to the present invention.
  • a coating composition which is particularly useful in preparing photographic elements comprises an aqueous hydrophilic colloid and the surfactant as described above.
  • the hydrophilic colloid is preferably gelatin.
  • Other hydrophilic colloids useful herein include modified gelatin, colloidal albumin, cellulose derivatives, polyvinyl alcohol, water-soluble polyacrylates, polyacrylamide and copolymers thereof.
  • a process of preparing a photographic element comprises coating a support such as film base such as poly(ethylene terephthalate), paper, glass or aluminium foil with at least one layer of a coating composition comprising a hydrophilic colloid and a surfactant according to the present invention.
  • a support such as film base such as poly(ethylene terephthalate), paper, glass or aluminium foil
  • a coating composition comprising a hydrophilic colloid and a surfactant according to the present invention.
  • the support is coated with a silver halide emulsion layer or layers and the layers of the coatings described above as well as any other layers useful therein simultaneously with a multicoating apparatus such as a bead coating apparatus.
  • the fluorosurfactants of the present invention are particularly useful in coatings for photographic elements because they have the ability to lower the surface tension of an aqeuous solution of gelatin to a value of less than 30 mN/m measured under static conditions at concentrations generally used for photographic products. Examples of such concentrations are from 0.03 to 0.5 weight/volume percent. This prevents non-uniformities in thickness of freshly coated layers caused by localized surface tension gradients.
  • the ability to provide a dried down gelatin layer into which it is incorporated in an amount equal to the critical micelle concentration with a highly wettable surface to aqueous processing solutions or other liquids applied to the surface during use may be assessed by measurement of contact angle.
  • the wettability of the surface may be defined in terms of an advancing contact angle, eA, It may be advantageous for the surface active agent to provide B A * 45° in respect of the surface when spread with pure water.
  • the surfactants of the present invention also have the ability to produce a uniform coating without repellency spots.
  • repellency is meant the round-shaped unevenness or hole in a coated layer which is produced by a small globule of surface active insoluble liquid in contact with the liquid-air interface during coating of the layer.
  • the control of coating uniformity is assessed by coating a pair of layers, the upper of which contains the surface active agent under test, onto a polyethylene terephthalate film base suitably subbed to give good adhesion to gelatin.
  • the bottom layer consists of a 4% solution of a bone gelatin in water coated at 85.4 millilitres/m 2 and the top layer consists of 7% bone gelatin with colloidal silver added to give a grey coloration (the gelatin being chosen as one containing natural fats or small droplets of liquids known to cause repellency spots) to which is added the surface active agent in an amount at or above the critical micelle concentration.
  • the coverage of the top layer is 14.2 millilitres/m 2 . Both layers are applied simultaneously at a temperature of 40°C using a conventional double slide hopper with applied suction and at a linear coating speed of 30 m/min.
  • the surface active agent is sufficiently soluble in an aqueous solution of gelatin (5% weight/ volume) for it not to remain as a separate phase in the solution. If the solubility of the surface active agent is insufficient to meet this requirement, the presence of a separate phase could result in the coating having a mottled appearance i.e. a non-uniform coating. The greater the insolubility of the surface active agent, the more non-uniform the coating becomes. In this case, the limiting concentration of the surface active agent is reached either very near to the critical micelle concentration or without micelle formation at all.
  • the surface active agent is not so soluble in the bulk aqueous phase that adsorption at the liquid-air interface takes place only with difficulty and then at high concentrations.
  • the surface active agent works at high concentration, its use at high concentrations is both uneconomical and undesirable.
  • the critical micelle concentration of the surface active agent occurs at a value of up to 0.5 g of the dry surface active agent per 100 ml of water.
  • the starting material for the preparation of the compound above was HC 6 F, Z CH Z OH which was commercially available.
  • the surface tension (static) of an aqueous solution of this surface active agent was measured as a function of bulk concentration with a Wilhelmy Blade surface Tensiometer. It was found that the surface tension was lowered to about 22mN/m at or above the critical micelle concentration (CMC).
  • the wettability was estimated from contact angle measurements on the dried down gelatin containing the surfactant. It was found that when the concentration of the surface active agent exceeded the critical micelle concentration the surface was wettable with both water and tetrachloroethylene (a liquid commonly applied to the surface during printing by the wet-gate-method).
  • a test coating of the surface active agent was carried out with the surface active agent added at concentrations of 0.02 and 0.2% weight/volume to the top layer of the two layer coating. At the higher concentration, repellency spots were completely supressed, no other coating imperfections were produced and a uniform coating resulted.
  • the surface active agent was added to a radiation-sensitive photographic emulsion, i.e. a gelatino photographic silver bromoiodide emulsion, and was tested for changes in sensitometric response from that of the coating without the surface active agent. The test indicated that the surface active agent was photographically inert.
  • the starting material and the preparation of the compound above were in accordance with the method described in Example 1 except that the amount of glycidol used was increased by an amount to provide the longer glycidyl chain length.
  • the surface tension (static) of an aqueous solution of the surface active agent was measured in accordance with Experiment 1 above and was found to be between 22 and 26mN/m at or above the CMC.
  • a test coating of the surface active agent at a concentration of 0.3% weight/volume was carried out and the resultant coating was completely free from repellency spots and was uniform in appearance.
  • the starting material for the preparation of the compound above was H(CF2)1,CH20H.
  • the preparation was carried out in accordance with the method described in Example 1 except that the amount of glycidol used was increased by an amount to provide the longer glycidyl chain length.
  • the surface tension (static) of an aqueous solution of the surface active agent was measured and was found to be approximately 26mN/m at or above the CMC.
  • a test coating of the surface active agent at a concentration of 0.1 % weight/volume was carried out and the coating was completely free from repellency spots and was uniform in appearance.
  • non-ionic surfactants containing fluorocarbon and polyglycidyl groups as described in GB-A-1,524,631 give highly variable results when they are used as coating aids.
  • the substitution of H(CF 2 ) 8 CH 2 O[glycidyl] 20 SO 3 NH 4 by either H(CF 2 ) 3 CH 2 0[glycidyl] 4 0H or H(CF 2 ) 10 CH 2 O[glycidyl] 20 OH in the test coating procedure of this Example provided coatings that were mottled and highly non-uniform.
  • Example 2 The compound above was prepared by a method analogous to that used in Example 1. It was tested and was found to possess properties similar to those found in Examples 1-3 and providing a figure of 18mN/m for surface tension.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polyethers (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (13)

1. Wasserlösliche oberflächenaktive Verbindung mit einer endständigen Fluorkohlenstoffgruppe, die über ein Bindeglied an eine Polyglycidylkette mit einer willkürlichen Mischung von Gruppen der Formeln
Figure imgb0019
gebunden ist und an die mindestens ein Anion gebunden ist, dem oder denen jeweils ein Kation zugeordnet ist.
2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß die endständige Fluorkohlenstoffgruppe direkt über ein Kohlenwasserstoffbindeglied an die Polyglycidylkette gebunden ist.
3. Verbindung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Anion ein Sulfatanion ist.
4. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß sie der folgenden Formel entspricht
Figure imgb0020
in der bedeuten:
Y eine Fluorkohlenstoffgruppe,
X ein Bindeglied aus einer Kohlenwasserstoffgruppe mit 1 bis 6 Kohlenstoffatomen, einer Ether-, Ester-, Amino-, Amido- oder Sulfonamidogruppe oder einer Kombination hiervon;
E eine Polyglycidylkette;
T' und T2 unabhängig voneinander an E gebundene anionische Gruppen;
M ein monovalentes Kation, das T1 oder T2 zugeordnet ist;
z gleich 0 oder eine Zahl von 1 bis zur maximalen Anzahl von Positionen an E, an die anionische Gruppen gebunden sein können;
y gleich 0 oder 1, wobei gilt, daß z und y mindestens gleich 1 ist;
x gleich 1 oder 2 und
u die Anzahl von Kationen, die erforderlich ist, um die verhandenen anionischen Gruppen zu neutralisieren.
5. Verbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Fluorkohlenstoffgruppe der folgenden Formel entspricht:
Figure imgb0021
in der A gleich H oder F ist und a für 4 bis 8, vorzugsweise 6 bis 8 steht.
6. Verbindung nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß das Bindeglied X eine ―CH2―Gruppe ist.
7. Verbindung nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß X der folgenden Formel entspricht:
Figure imgb0022
in der bedeuten: Z ein Ether-, Ester-, Amino-, Amido-, oder Sulfonamidobindeglied; D ein Ether- oder Aminobindeglied; c gleich 0 oder 1; m gleich 0 oder 1 und b gleich 0 oder 1, vorausgesetzt, daß, wenn b gleich 0 ist, c+m gleich 1 ist und wenn b gleich 1 ist, m gleich 0 und c gleich 0 oder 1 ist.
8. Verbindung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie der folgenden Formel entspricht:
Figure imgb0023
in der T' eine anionische Gruppe und M eine kationische Gruppe derstellen, A gleich H oder F ist und f für eine Zahl von 4 bis 8 und d für eine Zahl von 2 bis 30 steht.
9. Photographisches Element mit einem Schichtträger, der mindestens eine Schicht aufweist, die ein hydrophiles Kolloid und eine oberflächenaktive Verbindung enthält, dadurch gekennzeichnet, daß die oberflächenaktive Verbindung eine solche nach einem der Ansprüche 1 bis 8 ist.
10. Photographisches Element nach Anspruch 9, dadurch gekennzeichnet, daß auf den Träger mindestens eine photographische Silberhalogenidemulsionsschicht aufgetragen ist.
11. Verfahren zur Herstellung eines photographischen Elementes, bei dem man einen Schichtträger mit einer Beschichtungsmasse mit einem hydrophilen Kolloid und einer oberflächenaktiven Verbindung nach einem der Ansprüche 1 bis 8 beschichtet.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß man den Träger mit einer photographischen Silberhalogenidemulsionsschicht beschichtet.
EP82902078A 1981-07-13 1982-07-13 Anionische oberflächenaktive verbindungen, photographische elemente die diese verbindungen enthalten und verfahren zur herstellung der elemente Expired EP0083354B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8121480 1981-07-13
GB8121480 1981-07-13

Publications (2)

Publication Number Publication Date
EP0083354A1 EP0083354A1 (de) 1983-07-13
EP0083354B1 true EP0083354B1 (de) 1986-08-27

Family

ID=10523194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82902078A Expired EP0083354B1 (de) 1981-07-13 1982-07-13 Anionische oberflächenaktive verbindungen, photographische elemente die diese verbindungen enthalten und verfahren zur herstellung der elemente

Country Status (5)

Country Link
EP (1) EP0083354B1 (de)
JP (1) JPS58501075A (de)
CA (1) CA1254223A (de)
DE (1) DE3272885D1 (de)
WO (1) WO1983000162A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9010967D0 (en) * 1990-05-16 1990-07-04 Kodak Ltd Hydrophilic colloid composition for a photographic material
GB202006525D0 (en) * 2020-05-04 2020-06-17 Sphere Fluidics Ltd Surfactant

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3470258A (en) * 1967-04-19 1969-09-30 Stevens & Co Inc J P Fluorinated alcohols-glycidol addition products
GB1174707A (en) * 1967-05-26 1969-12-17 Gaf Corp Improvements in or relating to Coating Compositions
JPS589408B2 (ja) * 1974-02-13 1983-02-21 富士写真フイルム株式会社 写真感光材料
JPS5729691B2 (de) * 1975-03-15 1982-06-24
JPS5494319A (en) * 1978-01-09 1979-07-26 Konishiroku Photo Ind Co Ltd Silver halide photographic material
FR2458564A1 (fr) * 1979-06-07 1981-01-02 Oreal Nouveaux oligomeres tensio-actifs perfluores, procede pour les preparer et compositions les contenant

Also Published As

Publication number Publication date
WO1983000162A1 (en) 1983-01-20
DE3272885D1 (en) 1986-10-02
CA1254223A (en) 1989-05-16
EP0083354A1 (de) 1983-07-13
JPS58501075A (ja) 1983-07-07

Similar Documents

Publication Publication Date Title
US4266080A (en) Perfluoroalkylthioethyl ether derivatives
JP2713964B2 (ja) 写真塗布組成物
CA1129300A (en) Use of perfluoroalkane sulphonamide salts as surface active agents
EP0314425B1 (de) Nichtionische Oberflächenaktivverbindungen und photographische Stoffe, die sie enthalten
EP0363094B1 (de) Fluorchemische, oberflächenaktive Verbindungen und Verfahren zu deren Herstellung
EP0002004B1 (de) Verfahren zur Herstellung fluorhaltiger kationischer Verbindungen und ihre Verwendung als oberflächenaktive Mittel
JPS6143341B2 (de)
EP0083354B1 (de) Anionische oberflächenaktive verbindungen, photographische elemente die diese verbindungen enthalten und verfahren zur herstellung der elemente
JPS632951B2 (de)
JPS629586B2 (de)
US3725080A (en) Coating formulations containing the reaction product of glycidol polyethers and sulfating agents
EP0383347A2 (de) Verfahren zur Herstellung photographischer Materialien
JPS6254533B2 (de)
US4214102A (en) Amino-ether amphoteric surface-active compounds
EP0470101B1 (de) Nichtionische oberflächenaktivverbindungen
CA2033312A1 (en) Surface-active compounds having a perfluoroalkyl group and a nitrogen-containing aliphatic radical, a process for their preparation and their use
EP0603944B1 (de) Nichtionische Oberflächenaktivverbindungen
EP0527983B1 (de) Nichtionische Oberflächenaktivverbindungen
EP0527883B1 (de) Hydrophile kolloidzusammensetzung für photographisches material
US10792633B2 (en) Composition comprising a fluorine-containing surfactant
RU433867C (ru) Смачиватель дл полива желатиновых галогексеребр ных фотографических эмульсий
US6605423B2 (en) Method for preparing a silver halide photographic emulsion
SU1644071A1 (ru) Способ получени неионогенного смачивател дл светочувствительных композиций
EP0597289B1 (de) Photographische Zusammensetzung enthaltend einen Verdicker
JPS6187648A (ja) 含フツ素第四級アンモニウム化合物の製法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19830707

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3272885

Country of ref document: DE

Date of ref document: 19861002

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940627

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940706

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940825

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950713

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST