EP0058694A1 - Method of recovering a photographic addendum from a dispersion thereof. - Google Patents
Method of recovering a photographic addendum from a dispersion thereof.Info
- Publication number
- EP0058694A1 EP0058694A1 EP81902384A EP81902384A EP0058694A1 EP 0058694 A1 EP0058694 A1 EP 0058694A1 EP 81902384 A EP81902384 A EP 81902384A EP 81902384 A EP81902384 A EP 81902384A EP 0058694 A1 EP0058694 A1 EP 0058694A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersion
- active agent
- surface active
- water
- recovering
- 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.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 10
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 4
- -1 glycerol ester Chemical class 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 229920000136 polysorbate Polymers 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002266 Pluriol® Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- NWGKJDSIEKMTRX-BFWOXRRGSA-N [(2r)-2-[(3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)C1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-BFWOXRRGSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004668 long chain fatty acids Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- ZKBBQUFQDGOTBZ-UHFFFAOYSA-N sodium;1,2,3-tri(propan-2-yl)naphthalene Chemical compound [Na].C1=CC=C2C(C(C)C)=C(C(C)C)C(C(C)C)=CC2=C1 ZKBBQUFQDGOTBZ-UHFFFAOYSA-N 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- 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
- G03C7/32—Colour coupling substances
-
- 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
- G03C11/00—Auxiliary processes in photography
- G03C11/24—Removing emulsion from waste photographic material; Recovery of photosensitive or other substances
Definitions
- This invention relates to a method of recovering a photographic addendum from a dispersion thereof.
- a water- insoluble organic compound into a hydrophilic colloid layer of a photographic sheet material (which may or may not be light-sensitive) in such a way that the compound cannot diffuse within or away from that layer.
- a photographic sheet material which may or may not be light-sensitive
- One method which has been employed for preventing diffusion of an incorporated organic compound in a hydrophilic colloid layer comprises dispersing the compound in admixture with a high-boiling, water-immisible, organic solvent.
- a solvent which need not be liquid at room temperature, is often referred to, and is referred to herein, as an 'oil-former' (see for instance United Kingdom patent specification No. 541,589).
- This method is carried out by dispersing the mixture of organic compound and oil-former in an aqueous solution of the hydrophilic colloid with the aid of a surface active agent and subsequently mixing the dispersion so obtained with the other constituents of the coating composition to be used in forming the layer.
- a method which has been proposed for recovering water-insoluble photographic addenda from dispersions thereof in aqueous media containing a protainaceous colloid and a surface active agent comprises treating the dispersion with an enzyme to degrade the colloid, and a substance which causes precipitation of the addendum (see Research Disclosure September 1977, Item No. 16101).
- the substance causing precipitation may be a surface active agent of opposite charge.
- a method of recovering a water-insoluble organic compound from a dispersion of a mixture thereof with an oil-former in an aqueous medium containing a hydrophilic colloid and a surface active agent which comprises adding to the liquid dispersion an oleophilic non-ionic surface active agent so as to cause crystallization of the organic compound.
- the method of the invention is very suitable for the recovery of couplers and other compounds (such as redcx dye-releasing compounds) used for image formation in colour photographic materials from their dispersions, and is also useful for recovering such other organic compounds as ultra violet absorbers and dye stabilizing agents.
- couplers and other compounds such as redcx dye-releasing compounds
- References giving information on couplers are given in Section VII of Research Disclosure December 1973, Item 17643.
- the couplers commonly employed in photographic materials are water-insoluble compounds often containing ballast groups, phenolic (including naphtholic) couplers being used for producing cyan dyes and compounds containing an activated methylene group, including both heterocyclic and open-chain compounds, being used for producing magenta and yellow dyes.
- Important magenta couplers are pyrazolones and important yellow couplers are benzoylacetanilides.
- Patents describing couplers include the following United States Patents: Cyan dye-forming 2 367 531 3 034 892
- the compounds are substantially water-insoluble, high-boiling organic crystalloidal materials.
- esters including organic esters such as di-n-butyl phthalate, and phosphate esters, such as tricresyl phosphate.
- the oil-former preferably has a boiling point of at least 150oC and is chemically inert in the chosen system. Other desirable properties are listed in the U.K. Specification, together with numerous examples of suitable compounds.
- the non-ionic surface-active agent used in a method of the invention is oleophilic and preferably has a hydrophile-lipophile balance (HLB) value no greater than 5 but having such a value does not necessarily ensure that an agent will be satisfactory.
- HLB hydrophile-lipophile balance
- Methods of determining HLB are described in, for instance, 'Emulsion Science', P.Sherman, Academic Press, London (1968), Chapter 3. In many instances, the HLB of commercially available surface active agents is quoted by the suppliers. It may be noted that the maximum HLB value likely to be found for any surface active agent is approximately 40.
- Types of surface active agent which have been found effective for the method of the invention include: glycerol esters poiyoxyethylene ethers sorbitan esters. Commercial surface active agents of these types include certain of the agents sold under the trade marks:
- ncn-ionic surface active agent For a given dispersion, it is necessary to select an optimum ncn-ionic surface active agent and the optimum concentration thereof, by preliminary tasting with small quantities. A mixture of non-ionic surface active agents may in some cases give a synergistic effect.
- the amount of non-ionic surface active agent required is of the same order as the amou t of addendum and oil-former in the dispersion.
- the weight of surfactant required is usually from 0.1 to 10 times the total weight of addendum and oil-former.
- auxiliary solvents are ethyl and butyl acetates, and 2-(2-butoxyethoxy)ethyI acetate.
- the dispersion is if necessary liquified by melting and the ncn-ionic surface active agent added.
- Any auxiliary solvent to be used may be added at the same time or later. It is convenient when an auxiliary solvent is used to dissolve the surface active agent in this.
- the compound to be recovered After the compound to be recovered has crystallised, it may be filtered and washed with warm water to remove the hydrophilic colloid and any water soluble surface-active agent. It may also be washed with an organic solvent having a low solvent power for the compound being recovered but a high solvent power for the oleophilic surface active agent. Hydrocarbon solvents such as petroleum ether, hexane and heptane are suitable in many instances. Often, the dried recovered compound is sufficiently pure for reuse without further treatment.
- the invention is illustrated by the following
- Dispersion A The couplers, oil-formers and weights of anionic surfactant in the two dispersions were as follows: Dispersion A
- Cyan dye-forming coupler 2-[ ⁇ -(2,4-di-tert-amyl- phenoxy)-butyramido]-4,6- dichlcro-5-methylphenol.
- Oil former dibutylphthalate.
- Magenta dye-forming coupler 1- ( 2 , 4 , 6- trichlorophenyl ) - 3- ⁇ 5- [ ⁇ -3-tert-butyl-4- hydroxyphenoxy) tetradecane- amido]-2-chloroanilino ⁇ -5- pyrazolone .
- Oil former tricresylphosphate Weight of anionic surfactant : 5.0 g.
- R is a long-chain fatty acid group of 12 to 18 carbon atoms.
- 'Alkanol XC' is believed to be sodium triisopropyl naphthalene sulphonate.
- the mixture obtained was stirred at 50°C for 8 hours and the precipitated coupler filtered off and washed successively with hot water and heptane.
- the coupler was recovered in 57% yield and was at least as pure as when incorporated into the original dispersion (measured by high pressure liquid chromatography).
- the effectiveness of two cationic surface active agents at causing crystallisation of coupler from the dispersions A and 3 used for Example 1 was examined.
- the cationic agents were: (i) cetyl pyridinium chloride (ii) didodecyldimethylammonium bromide.
- 10 ml of a 1% w/v aqueous solution of the cationic agent was added to 4 ml of the dispersion and held at 40°C. Samples were examined after 2 and 24 hours using a microscope at X200 magnification and with crossed polarizing filters. The numbers and sizes of crystals observed are expressed qualitatively in the following table.
- the dispersion A sample treated with cationic surfactant (i) for 24 hours was filtered and the coupler crystals collected represented a recovery of less than 25%.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Un additif photographique organique insoluble a l'eau est recupere depuis une dispersion d'un melange de celui-ci avec un formeur d'huile dans un milieu aqueux contenant un colloide hydrophile et un agent tensio-actif par addition d'un agent tensio-actif oleophile non ionique selectionne.A water-insoluble organic photographic additive is recovered from a dispersion of a mixture thereof with an oil former in an aqueous medium containing a hydrophilic colloid and a surfactant by addition of a surfactant. selected non-ionic oleophilic active ingredient.
Description
METHOD OF RECOVERING A PHOTOGRAPHIC ADDENDUM FROM A
DISPERSION THEREOF
This invention relates to a method of recovering a photographic addendum from a dispersion thereof.
It is oftan necessary to incorporate a water- insoluble organic compound into a hydrophilic colloid layer of a photographic sheet material (which may or may not be light-sensitive) in such a way that the compound cannot diffuse within or away from that layer. For example, in a colour photographic material having superimposed red-, green- and blue-sensitive gelatino-silver halide emulsion layers containing, respectively, cyan, magenta and yellow dye-forming couplers it is essential that these couplers remain in their respective layers. If they do not, the image produced in each layer is not of τhe appropriate pure subtractive primary colour hut is of a mixture of dyes giving unwanted absorption. One method which has been employed for preventing diffusion of an incorporated organic compound in a hydrophilic colloid layer comprises dispersing the compound in admixture with a high-boiling, water-immisible, organic solvent. Such a solvent, which need not be liquid at room temperature, is often referred to, and is referred to herein, as an 'oil-former' (see for instance United Kingdom patent specification No. 541,589). This method is carried out by dispersing the mixture of organic compound and oil-former in an aqueous solution of the hydrophilic colloid with the aid of a surface active agent and subsequently mixing the dispersion so obtained with the other constituents of the coating composition to be used in forming the layer. If,
through being stored too long or for other reasons, a dispersion does not have the required characteristics, it is desirable to recover the dispersed compound therefrom so that it may be reused. A method which has been proposed for recovering water-insoluble photographic addenda from dispersions thereof in aqueous media containing a protainaceous colloid and a surface active agent, comprises treating the dispersion with an enzyme to degrade the colloid, and a substance which causes precipitation of the addendum (see Research Disclosure September 1977, Item No. 16101). In the case where an ionic surface active agent is present, the substance causing precipitation may be a surface active agent of opposite charge. Whilst this method is capable of giving satisfactory results with coupler and ether dispersions, it has the disadvantage of employing an enzyme which must be eliminated completely from the recovered addendum to prevent degradation of any colloid in which the addendum is subsequently to be dispersed. According to the present invention there is provided a method of recovering a water-insoluble organic compound from a dispersion of a mixture thereof with an oil-former in an aqueous medium containing a hydrophilic colloid and a surface active agent, which comprises adding to the liquid dispersion an oleophilic non-ionic surface active agent so as to cause crystallization of the organic compound.
The method of the invention is very suitable for the recovery of couplers and other compounds (such as redcx dye-releasing compounds) used for image formation in colour photographic materials from their dispersions, and is also useful for recovering such other organic compounds as ultra violet absorbers and dye stabilizing agents.
References giving information on couplers are given in Section VII of Research Disclosure December 1973, Item 17643.
The couplers commonly employed in photographic materials are water-insoluble compounds often containing ballast groups, phenolic (including naphtholic) couplers being used for producing cyan dyes and compounds containing an activated methylene group, including both heterocyclic and open-chain compounds, being used for producing magenta and yellow dyes. Important magenta couplers are pyrazolones and important yellow couplers are benzoylacetanilides. Patents describing couplers include the following United States Patents: Cyan dye-forming 2 367 531 3 034 892
2423 730 3 311 476
2 474 293 3 419 390
2772 162 3 458 315 2895 826 3 476 563 Magenta dye-forming
2343703 3 062 653
2 369 489 3 127 269
2 600 7S3 3 311 476
2908 573 3 419 391 2933 391 3 518 429
Yellow dye-forming 2 298 443 3 277 155
2407 210 3 408 194
2875 057 3 415 652 2906 573 3 447 923
3 265 506 3 933 501
An account of dye-forming development is given in 'Modem Photographic Processing', Vol. 2 , Grant Haist, Wiley, New York, 1978, Chapter 9.
A great variety of compounds may be used as oil-formers in coupler dispersions, as described in United Kingdom Patent Specification No. 541,539. The compounds are substantially water-insoluble, high-boiling organic crystalloidal materials. Particularly suitable are esters, including organic esters such as di-n-butyl phthalate, and phosphate esters, such as tricresyl phosphate. The oil-former preferably has a boiling point of at least 150ºC and is chemically inert in the chosen system. Other desirable properties are listed in the U.K. Specification, together with numerous examples of suitable compounds.
The non-ionic surface-active agent used in a method of the invention is oleophilic and preferably has a hydrophile-lipophile balance (HLB) value no greater than 5 but having such a value does not necessarily ensure that an agent will be satisfactory. Methods of determining HLB are described in, for instance, 'Emulsion Science', P.Sherman, Academic Press, London (1968), Chapter 3. In many instances, the HLB of commercially available surface active agents is quoted by the suppliers. It may be noted that the maximum HLB value likely to be found for any surface active agent is approximately 40. Types of surface active agent which have been found effective for the method of the invention include: glycerol esters poiyoxyethylene ethers sorbitan esters. Commercial surface active agents of these types include certain of the agents sold under the trade marks:
'Arlacel', 'Brij', 'Emerest',
'Grindtek',
'Pluriol',. 'Pluronic', 'Span'. For a given dispersion, it is necessary to select an optimum ncn-ionic surface active agent and the optimum concentration thereof, by preliminary tasting with small quantities. A mixture of non-ionic surface active agents may in some cases give a synergistic effect. The amount of non-ionic surface active agent required is of the same order as the amou t of addendum and oil-former in the dispersion. Thus the weight of surfactant required is usually from 0.1 to 10 times the total weight of addendum and oil-former.
In some instances, the extraction of the compound to be recovered can be facilitated by addition either of a slightly water soluble organic solvent of the kind sometimes referred to as an 'auxiliary solvent' (see, for instance, U.K. Patent No. 791,219). Examples of auxiliary solvents are ethyl and butyl acetates, and 2-(2-butoxyethoxy)ethyI acetate.
In carrying out a method of the invention, the dispersion is if necessary liquified by melting and the ncn-ionic surface active agent added. Any auxiliary solvent to be used may be added at the same time or later. It is convenient when an auxiliary solvent is used to dissolve the surface active agent in this.
After the compound to be recovered has crystallised, it may be filtered and washed with warm
water to remove the hydrophilic colloid and any water soluble surface-active agent. It may also be washed with an organic solvent having a low solvent power for the compound being recovered but a high solvent power for the oleophilic surface active agent. Hydrocarbon solvents such as petroleum ether, hexane and heptane are suitable in many instances. Often, the dried recovered compound is sufficiently pure for reuse without further treatment. The invention is illustrated by the following
Examples: Example 1
A 10 g sample of each of two coupler dispersions was melted and made up to a volume of 30 ml with distilled water. Each dispersion had the approximate composition: coupler 100 g oil-former 50 g gelatin 100 g anionic surfactant* see table below other constituents and water to make 1000 g
*a sodium naphthalene sulphonate.
The couplers, oil-formers and weights of anionic surfactant in the two dispersions were as follows:
Dispersion A
Cyan dye-forming coupler: 2-[α-(2,4-di-tert-amyl- phenoxy)-butyramido]-4,6- dichlcro-5-methylphenol. Oil former: dibutylphthalate.
Weight of anionic surfactant 3.5 g.
Disnersion B
Magenta dye-forming coupler : 1- ( 2 , 4 , 6- trichlorophenyl ) - 3- { 5- [ α -3-tert-butyl-4- hydroxyphenoxy) tetradecane- amido]-2-chloroanilino }-5- pyrazolone . Oil former : tricresylphosphate Weight of anionic surfactant : 5.0 g.
A 1 ml quantity of a solution of 1 volume of the surfactant ' Pluronic L121 ' (trade mark) in two volumes of 2- ( 2-butoxyethoxy) ethyl acetate was stirred in. 'Pluronic L121 ' is believed to have the structure :
HO ( CH2CH2O ) a ( CHCH2O)b ( CH2 H2O) CH CH3 wherein (a - c) is approximately 10 and b is approximately 70 , and has an HLB of about 0.5. The dispersion was held at 50°C for ten minutes and then 4 ml of the surface active agent 'Triton X-100', believed to have the structure:
was added. The mixture was diluted to 120 ml, held at 50°C for 1 hour and the recovered coupler then filtered off and washed with water. In each case the recovery rate was 80% and the coupler recovered was at least as pure as that used in preparing the original dispersion. Example 2
Twenty grams of a dispersion of the magenta dye dye-forming coupler 1-(4,6-dichloro-2-methoxyphenyI)-3- [α-(3-n-pentadecylphenoxy)butyτamido]-5-pyrazolone, this dispersion having the approximate composition: coupler 100 g oil-former (tricresylphosphate) 50 g gelatin 100 g anionic surfactant ('Alkanol XC') 3 g other constituents and water to make 1000 g was mixed with 20 g of water and with 4 g of a mixture of 2 g 'Witcamide 511' (trade mark) and 2 g of 10% aqueous solution of 'Alkanol XC' (trade mark). 'Witcamide 511' is a non-ionic surface active agent believed to be of the formula:
wherein R is a long-chain fatty acid group of 12 to 18 carbon atoms. 'Alkanol XC' is believed to be sodium triisopropyl naphthalene sulphonate. The mixture obtained was stirred at 50°C for 8 hours and the precipitated coupler filtered off and washed successively with hot water and heptane. The coupler was recovered in 57% yield and was at least
as pure as when incorporated into the original dispersion (measured by high pressure liquid chromatography). This method was repeated on a multi-kilogram scale, the only changes in procedure being that when crystallization was complete (as judged by microscopic examination) a volume of heptane equal to the volume of 'Witcamide' used was added and the mixture then stirred for a further 3 hours before the recovered coupler was filtered off and washed, the yield and the purity of the product were at least as satisfactory as for the small scale trial. Example 3
This is a comparative Example. The effectiveness of two cationic surface active agents at causing crystallisation of coupler from the dispersions A and 3 used for Example 1 was examined. The cationic agents were: (i) cetyl pyridinium chloride (ii) didodecyldimethylammonium bromide. In each test, 10 ml of a 1% w/v aqueous solution of the cationic agent was added to 4 ml of the dispersion and held at 40°C. Samples were examined after 2 and 24 hours using a microscope at X200 magnification and with crossed polarizing filters. The numbers and sizes of crystals observed are expressed qualitatively in the following table.
The dispersion A sample treated with cationic surfactant (i) for 24 hours was filtered and the coupler crystals collected represented a recovery of less than 25%.
It is evident that even the more effective of the cationic surfactants was slower and less efficient than an oleophilic non-ionic surfactant as required for the method of the present invention.
Claims
1. A method of recovering a water-insoluble organic compound from a dispersion of a mixture thereof with an oil-former in an aqueous medium containing a hydrophilic colloid and a surface active agent, which comprises adding to the liquid dispersion an oleophilic non-ionic surface active agent so as to cause crystallization of the organic compound.
2. A method according to claim 1 wherein the non-ionic surface-active agent is a glycerol ester, polyoxyethylene ether or sorbitan ester.
3. A method according to claim 1 or 2 wherein a second non-ionic surface-active agent is added to the dispersion.
4. A method according to any of the preceding claims wherein the water-insoluble organic compound to be recovered is a dye-forming coupler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8028150 | 1980-09-01 | ||
| GB8028150 | 1980-09-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0058694A1 true EP0058694A1 (en) | 1982-09-01 |
| EP0058694B1 EP0058694B1 (en) | 1985-07-10 |
Family
ID=10515760
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81902384A Expired EP0058694B1 (en) | 1980-09-01 | 1981-09-01 | Method of recovering a photographic addendum from a dispersion thereof |
| EP81303984A Pending EP0047170A1 (en) | 1980-09-01 | 1981-09-01 | Method of recovering a photographic addendum from a dispersion thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81303984A Pending EP0047170A1 (en) | 1980-09-01 | 1981-09-01 | Method of recovering a photographic addendum from a dispersion thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | UST102402I4 (en) |
| EP (2) | EP0058694B1 (en) |
| JP (1) | JPS57501347A (en) |
| DE (1) | DE3171315D1 (en) |
| WO (1) | WO1982000901A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU589614B2 (en) * | 1985-04-05 | 1989-10-19 | Konishiroku Photo Industry Co., Ltd. | Method of treating photographic waste solutions and automatic photograph processor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1274048A (en) * | 1969-07-30 | 1972-05-10 | Bayer Ag | Process for the production of pure basic dyestuffs |
| IT1066378B (en) * | 1976-02-24 | 1985-03-04 | Betz Int | IMPROVEMENT IN THE SEPARATION PROCESS BY FLOTATION |
| JPS5427428A (en) * | 1977-08-03 | 1979-03-01 | Fuji Photo Film Co Ltd | Recovery method of oil soluble couplers |
-
1981
- 1981-09-01 WO PCT/GB1981/000174 patent/WO1982000901A1/en active IP Right Grant
- 1981-09-01 DE DE8181902384T patent/DE3171315D1/en not_active Expired
- 1981-09-01 JP JP56502820A patent/JPS57501347A/ja active Pending
- 1981-09-01 EP EP81902384A patent/EP0058694B1/en not_active Expired
- 1981-09-01 EP EP81303984A patent/EP0047170A1/en active Pending
-
1982
- 1982-04-29 US US06/373,193 patent/UST102402I4/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8200901A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU589614B2 (en) * | 1985-04-05 | 1989-10-19 | Konishiroku Photo Industry Co., Ltd. | Method of treating photographic waste solutions and automatic photograph processor |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3171315D1 (en) | 1985-08-14 |
| WO1982000901A1 (en) | 1982-03-18 |
| JPS57501347A (en) | 1982-07-29 |
| EP0047170A1 (en) | 1982-03-10 |
| EP0058694B1 (en) | 1985-07-10 |
| UST102402I4 (en) | 1982-11-02 |
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