US2639990A - Process for improving the whiteness or color of materials and products resulting therefrom - Google Patents
Process for improving the whiteness or color of materials and products resulting therefrom Download PDFInfo
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- US2639990A US2639990A US165116A US16511650A US2639990A US 2639990 A US2639990 A US 2639990A US 165116 A US165116 A US 165116A US 16511650 A US16511650 A US 16511650A US 2639990 A US2639990 A US 2639990A
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- Prior art keywords
- phenyl
- materials
- alkyl
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- Prior art date
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- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title description 15
- 239000007850 fluorescent dye Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 61
- 150000001875 compounds Chemical class 0.000 description 41
- 125000000217 alkyl group Chemical group 0.000 description 33
- 229910052736 halogen Inorganic materials 0.000 description 23
- 150000002367 halogens Chemical class 0.000 description 23
- 125000003545 alkoxy group Chemical group 0.000 description 16
- 125000001424 substituent group Chemical group 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- -1 1 -sulphophenyl-3-p-phenoxyphenyl-5-phenyl pyrazoline Chemical compound 0.000 description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 11
- 239000004753 textile Substances 0.000 description 11
- 239000000123 paper Substances 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JFJWVJAVVIQZRT-UHFFFAOYSA-N 2-phenyl-1,3-dihydropyrazole Chemical compound C1C=CNN1C1=CC=CC=C1 JFJWVJAVVIQZRT-UHFFFAOYSA-N 0.000 description 1
- FNZBVOIGOZBHCS-UHFFFAOYSA-N 5,5-diphenyl-1,4-dihydropyrazole Chemical compound C1C=NNC1(C=1C=CC=CC=1)C1=CC=CC=C1 FNZBVOIGOZBHCS-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SRBFZHDQGSBBOR-HWQSCIPKSA-N L-arabinopyranose Chemical compound O[C@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-HWQSCIPKSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003599 detergent 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
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the foregoing definition of the compounds does not include compounds in which R1 or Arc 5 dfersfitlood tetxtlle materials generally, 1n till: ntains a mtro substltuent, or 1n which An cong g mgg g gg z' z ifi gg 3 g z tains a sulphonic carboxylic nitro or cyano group Y since those compounds do not fluoresce.
- the free carboxylic and sulphonic acids gi i fi g iud d pogntiers 1 fib l m;- are substantive to protein and polyamlde fibres teriais sllch 22 1 g d g g gfi i z and films, but for the other materials, e. g. cellu losic materials such as cotton and paper, an $2135 :zmgg zf z i gf i ggfi i gi %gg cellulose acetate materials, the alkali salts are generally preferred. arias 221:3212?marria es: 5"?
- M.P.,C from compacted fibres, e. g. paper, cardboard, 25 l g- %p y l ps ra e felt and the like, or from natural colloids such j f l f f gggggfgg as gelatin.
- a process 1:5-6 phenyl-3-p-eth0xyphenyl pyraz011ne 13% for improving fibres and films comprises applyiz2 itfifitiiii?t ititiiit fitlh ttittie::::::: its ing thereto a small quantity Of a.
- R1 is a' 'hydroge'n'atom, hydrocarbon kfigiifilg fifigfifififig1it?t;onn roup or substitutedhydrocarbon group,
- phenyl or naphthyl I p su1ph0phenyl 31,401yl 5 phem,lpymzoline which may contain any of the substituents hyl-psulgfiopgenyl-gg-nigthoiiylphfliylgihleiiyl pg-lz'ilziollne n-p-su op eny- -e oxy eny -o-p e y pyr ne droxy F hydFoxya'lkyl' p hydrocar' 1 -sulphophenyl-3-p-phenoxyphenyl-5-phenyl pyrazoline bon-substituted-ammo or acylammo groups or 1-p-Su%pg0plfienyl-g-(g-phingl)phiiilyl iplhenyil pyrazolline .-p-su p o
- WhlOh compound is colourless in aqueous i inetliyll-os ulghgflillienylg 59 111 11 fiiyralzolme 1,
- T 2 1-(4 8-disulphonaphthyl-2l-3 5-diphenyl pyrazoline less in aqueous or ethyl alcoholic solution
- 1s 5
- p-sulphophen yl-3pl1enyl-5-a-furylpyrazohne meant that a solution of the compound in water 5 1 Pymzohne or ethyl alcohol has an absorption maximum not greater than 4000' A.
- the preferred compounds according to the" present invention are those in which the pyrazoline contains a sulphophenyl group in the 1-posi tion and contains in the 3- and 5-positions phenyl groups or substituted phenyl groups.
- the compounds may be prepared by various methods.
- One method is described in co-pending application Serial No. 165,118, filed on even date herewith.
- A. second method consists in the condensation of a Mannich reaction product (ob tained from an acetophenone with formaldehyde and an amine) with an aryl hydrazine
- the whiteness of textile materials, paper and the like can be very considerably enhanced by treating the materials with a solution of one of the said compoundsin water or an organic solvent, e. g. at a solution concentra tion of 1 part in 5000 to 1 part in 100,000.
- the compound in which R1 or Arz contains a sulphonic acid group may be used from weakly acid solution or even neutral solution and are substantive to wool from such solutions.
- the 10 partsjof bath will contain 0.0001 part of fiuorescer, i. e.,- one part of fibre takes up 0.0001 part of fluorescer. which is 0.01%. Therefore from the figures of l to 5,000 and. 1 to 100,000
- the compounds of this invention may be applied thereto at any stage in the manufacture of such materials.
- the compounds of this invention may be incorporated in such compositions before extrusion or casting so that they are uniformly dispersed throughout the products.
- the preferred fibres or films may be treated with solutions of the compounds.
- the compounds may be included in any of the liquids commonly employed for dyeing, scouring, dressing and the like, and this invention includes compositions for application to textiles for such purposes which include a compound of the" foregoing formula. in conjunction with a textile dye,
- the compounds may be applied to the materials after the normal processes of their manufacture have been completed, for example by including the compounds in domestic washing preparations.
- the compounds may be applied to the wood pulp or rag-fibre before such material is made into paper, or during the paper-making operation, or may be applied as a solution directly to the raw paper, or may be applied in a dressing composition, e. 'g. a baryta coating, applied to the paper.
- a dressing composition e. 'g. a baryta coating
- One important application of the invention is in the treatment of photographic prints'where application of a solution of a compound of the foregoing general formula has the effect of whitening the highlights of the print.
- Considerable effort has hitherto been directed to the produc--- tion of prints having brilliant highlights, and the present invention provides a simple method whereby this result may be achieved.
- the compounds may, if desired, be incorporated in the photographic emulsions, or sub-coat or supercoat layers, prior to coating such layers to form the photographic element.
- the tone may be changed to resemble very closely the cold tone commonly associated with prints made on paper coated with silver chloride emulsions.
- the compounds of this invention may also be applied to films coated on supports, for example to finished photographic films or plates where the gelatin film takes up the compound and is photographic thereby caused to fluoresce and the image to appear colder in tone.
- a process 'for improving fibres and films which comprises applying thereto a dispersion in a liquid medium of a white fluorescent compound of the general formula:
- R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents
- Ara is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
- a process for improving fibres and films which comprises applying thereto an aqueous solution of a white fluorescent compound of the general formula:
- R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents
- M2 is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
- a process for improving fibres and films which comprises applying thereto an aqueous solution of a fluorescent compound of the general formula:
- R1 is selectedfrom the class consisting of the hydrogen atom, alkyl, unsubstituted 61' phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- ,Ar1 is selected from the class consisting of. unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy 1 and phenoxy substituents
- A12 is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl,-sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by'weight of the said compound.
- a process for improving the whiteness of wool fibres and woollen textile materials which comprises applying thereto an aqueous solution of a compound of the general formula:
- R1 is a sulphonated phenyl group
- An is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and
- Arz is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
- R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents
- An is selected from the class, consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic andacetylamino substituents.
- Photographic light-sensitive materials having adsorbed thereto 0.01 to 1% by weight of a fluorescent compound of the general formula:
- R1 is selected from the classconsisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, AT]. is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and 'Alz is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents.
- Photographic printing paper having adsorbed thereto 0.01 to 1% by weight of a compound of the general formula:
- R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents
- Arz is selected from. the class consisting of unsubstituted phenyl and,
- R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents
- Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents
- Ar: i selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and' acetylamino substituents, so that the said fibres 8 and films absorb 0.01 to 1% by weighto! the said compound.
- a process for improving fibres and, films which comprises applying thereto a dispersion in a liquid medium of a white fluorescent compound of the general formula:
- R1 is selected from the class consisting of the hydrogen atom, methyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl and sulphophenyl groups
- X1 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, methoxy, ethoxy and phenoxy
- X2 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, sulphonic and acetylamino groups, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
- R1 is selected from the class consisting of the hydrogen atom, methyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl and sulphophenyl groups
- X1 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, methoxy, ethoxy and phenoxy
- X2 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, sulphonic and acetylamino groups.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Coloring (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
Description
Patented May 26, 1953 PROCESS FOR IMPROVING THE WHITENESS OR COLOR OF MATERIALS AND PRODUCTS RESULTING THEREFROM John David Kendall and George Frank Duffin, Ilford, England, assignors to Ilford Limited, Ilford, England, a British company No Drawing. Application May 29, 1950, Serial No. 165,116. In Great Britain June 3, 1949 13 Claims. (Cl. 95-7) OFFICE This invention relates to a process for the improvement of natural or synthetic fibrous ma terials and of films of natural or synthetic c01- loid materials. Within these terms are to be unz are those in which the absorption maximum does not exceed 3900 A.
The foregoing definition of the compounds does not include compounds in which R1 or Arc 5 dfersfitlood tetxtlle materials generally, 1n till: ntains a mtro substltuent, or 1n which An cong g mgg g gg z' z ifi gg 3 g z tains a sulphonic carboxylic nitro or cyano group Y since those compounds do not fluoresce. or of synthetic materials such as regenerated Compounds of the foregoing formula in which cellulose, cellulose nitrate, cellulose acetate, cellu- R1 or the group An are hydrocarbon radicleslose propionate cemtlose butyrate and mixed 10 containing substituent carboxylic or sulphonic celulose esters as, for instance, cellulose acetateacid groups are for many purposes particularly ti gi a s ?g z fg; favourable, since they form alkali metal and amg e riv tiv eg sui l i as vi fiyl esi ei's :02:5 iilo d s moniumsaltslwhich are substantive to pracmcany the whole range of fibresand films referredto 23 g i polymeng 9 1 lmatenalg p i above. The free carboxylic and sulphonic acids gi i fi g iud d pogntiers 1 fib l m;- are substantive to protein and polyamlde fibres teriais sllch 22 1 g d g g gfi i z and films, but for the other materials, e. g. cellu losic materials such as cotton and paper, an $2135 :zmgg zf z i gf i ggfi i gi %gg cellulose acetate materials, the alkali salts are generally preferred. arias 221:3212?marria es: 5"? of ma be used in accor ance wi h e resen nfilms of cellulose acetate, cellulose nitrate, cellu-- veniion p lose acetate-butyrate and the like, or formed M.P.,C from compacted fibres, e. g. paper, cardboard, 25 l g- %p y l ps ra e felt and the like, or from natural colloids such j f l f f gggggfgg as gelatin. 1-m-tolyl-3-phenyl pgrazoline 183 The foregoing materials and materials of simil-ygfigggi-gyf ggg gggg Fifi 3 lar character are hereinafter referred to for brevggipgenyl-g-mitlliyll ram iine g H 1 V 1p eny -po y pyrazo me my as fipres films 1: -diphenyl-3-p-methoxyphenyl pyrazo1ine -M- 142 According to the present invention a process 1:5-6 phenyl-3-p-eth0xyphenyl pyraz011ne 13% for improving fibres and films comprises applyiz2 itfifitiiii?t ititiiit fitlh ttitttie:::::::: its ing thereto a small quantity Of a. fluorescent 00m- 1 :l5-dipl1enyl-3-(p-ethoxy m -.methyl)phenyl pyrazo- 13 c ine I 5 pound of the genera-'1 'lormula" 1-phenyl-3 5-di(p-ch1orphenyl)phenyl pyrazoline 151 HZO- C AU 1: 3-diphenyl-5-p-methoxyphenyl pyrazoline 124 l.-phenyl-3-p-methoxyphnyl-5-p-tolyl pyrazoline 127 R1 1-pheny1-3-p-tolyl-5-p-methoxypheny1 pyrazoline 141 1-phenyl-3 5-di(p-methoxy)phenyl yrazohne 147 1 4-di(1' 3'-diphenyl pyrazolinyl-o)benzene 290 Examples of water-soluble compounds which i 40 can be used are:
2 wherein R1 is a' 'hydroge'n'atom, hydrocarbon kfigiifilg fifigfifififig1it?t;onn roup or substitutedhydrocarbon group, An 1s l-g-p fi y u p ggl sg g-g yl igggg .--supope y-- y-- y anaromatic residue, e. g. phenyl or naphthyl, I p su1ph0phenyl 31,401yl 5 phem,lpymzoline which may contain any of the substituents hyl-psulgfiopgenyl-gg-nigthoiiylphfliylgihleiiyl pg-lz'ilziollne n-p-su op eny- -e oxy eny -o-p e y pyr ne droxy F hydFoxya'lkyl' p hydrocar' 1 -sulphophenyl-3-p-phenoxyphenyl-5-phenyl pyrazoline bon-substituted-ammo or acylammo groups or 1-p-Su%pg0plfienyl-g-(g-phingl)phiiilyl iplhenyil pyrazolline .-p-su p op eny -p eny p-me oxyp eny pyrazo me halogen atoms and Am 15 an aromatic nucleus 1w henyl-s- ;t0iy1-5- -methox hen q pyrazoline which may contain any substituent groups, e. g. llrp isliillzlll ophenlylt-lli :12-(11(1nethgxyp{1eny1) r z i le 1 -p-su p op eny -p eny -pyrazo my enzene substltuent hydrocarbon hydroxy l by l-m-sulphophenyl 3:5-di(p-chlorphenyl) pyrazoline droxyalkyl, ammo, hYdIOCEtIbOIl SUbSlJliUlZGdl-m-sulplfiopiienyl-g-(gghfinyl){)henyl-5fphenyl pyrazolme ..-m-sup op eny 2 1p eny pyrazo 1116 Su1phoI nc carboxyh? or cyano v Hp-methyl-m-sulpho)phenyl-3 5-diphenyl pyrazoline groups, WhlOh compound is colourless in aqueous i inetliyll-os ulghgflillienylg 59 111 11 fiiyralzolme 1,
u -sup 0- 1 1c or p eny- :o- 1 eny pyrazo me or alcohohc solutlon- By term T 2 1-(4 8-disulphonaphthyl-2l-3 5-diphenyl pyrazoline less in aqueous or ethyl alcoholic solution 1s 5 1-p-sulphophen yl-3pl1enyl-5-a-furylpyrazohne meant that a solution of the compound in water 5 1 Pymzohne or ethyl alcohol has an absorption maximum not greater than 4000' A. The preferre d compounds 1-p-to1yl-3-phenyl-5-o-sulphopl1enyl pyrazoline l.-p-anetamidophenyl-3-pheny1-5-0-sulphophenyl pyrazoline The preferred compounds according to the" present invention are those in which the pyrazoline contains a sulphophenyl group in the 1-posi tion and contains in the 3- and 5-positions phenyl groups or substituted phenyl groups.
The compounds may be prepared by various methods. One method is described in co-pending application Serial No. 165,118, filed on even date herewith. A. second method consists in the condensation of a Mannich reaction product (ob tained from an acetophenone with formaldehyde and an amine) with an aryl hydrazine, and a third method is the condensation of a ketone of the type Ar-CO-C(R)=CHz with an aryl hydrazine.
Compounds of the foregoing general formula which are colourless, white or pale yellow have been found to possess a strong bluish fluorescence in daylight and a slightly less fluorescence in incandescent electric or similar light, and on appli cation to fibres and films they impart such fluorescence to them. The effect of applying these compounds to fibres and films is to impart a degree of brilliance to them which is attractive and. useful.- Applied to materials which are allegedly white, but of which the whiteness has a slight tinge of yellow or brown, the compounds serve to kill the yellow or brown tinge so that the apparent whiteness of the materials is very apprc ciably enhanced. This application of the materials is of especial importance, and the present invention is therefore particularly concerned with the application of the compounds to such offwhite fibres and films. It is a special advantage of the compounds 01' this invention, and especially those in which R1 or An contain a sulphom'c group, that they impart a. very desirable wl1ite ness to wool fibres, the effect being a strong resistance to fading under the action of light and a strong resistance to laundering.
Applied to dyed textile materials the com pounds have the effect of improvingthe apparent purity of the colour.
Very small quantities of the compounds are sufficient to achieve the desired improvement in the materials. Thus the whiteness of textile materials, paper and the like can be very considerably enhanced by treating the materials with a solution of one of the said compoundsin water or an organic solvent, e. g. at a solution concentra tion of 1 part in 5000 to 1 part in 100,000. Applied to wool, the compound in which R1 or Arz contains a sulphonic acid group may be used from weakly acid solution or even neutral solution and are substantive to wool from such solutions.
In order to convert the solution concentration of l in 5,000 and 1 in 100,000 o percent of compound absorbed by weight it must be assumed that the ratio of fibre to dye bath ranges from 1 to to l to 50 .andthat the dye bath is operated to exhaustion. Both of these assumptions are customary dyeing practice. Thus, taking the strongest solution envisaged, i in 5,000 and the greatest ratio of dye bath to fibre (50:1), one obtains the conditions in which the greatest amount of dye will be absorbed. In this case 50 parts of dye bath will contain 0.01 part of fluorescent compound, i. e., one part of fibre takes up 0.01 part of fluorescer, which is 1%..
Taking, on the other hand. the most dilute bath of 1 in 100,000 and the lowest ratio of fibre (10:1). the 10 partsjof bath will contain 0.0001 part of fiuorescer, i. e.,- one part of fibre takes up 0.0001 part of fluorescer. which is 0.01%. Therefore from the figures of l to 5,000 and. 1 to 100,000
4 and the normal dyeing practice an absor tion computation of 0.01 to 1% is calculated.
'In' the case of fibresor films which are not in their natural state, the compounds of this invention may be applied thereto at any stage in the manufacture of such materials. Thus in the production of artificial filaments, fibres or films by the extrusion or casting of colloid compositions, the compounds of this invention may be incorporated in such compositions before extrusion or casting so that they are uniformly dispersed throughout the products.
Alternatively the preferred fibres or films may be treated with solutions of the compounds. Thus in the treatment of textile materials the compounds may be included in any of the liquids commonly employed for dyeing, scouring, dressing and the like, and this invention includes compositions for application to textiles for such purposes which include a compound of the" foregoing formule. in conjunction with a textile dye,
detergent or other material used for treating textiles. The compounds may be applied to the materials after the normal processes of their manufacture have been completed, for example by including the compounds in domestic washing preparations.
In the case of paper and similar materials the compounds may be applied to the wood pulp or rag-fibre before such material is made into paper, or during the paper-making operation, or may be applied as a solution directly to the raw paper, or may be applied in a dressing composition, e. 'g. a baryta coating, applied to the paper.
The compounds referred to above in which neither R3 nor Ar: contains a sulphonlc or carbcxylic group fluoresce strongly in organic solvents and may be applied to protein and polyamide fibres from an organic solvent or aqueous organic solvent, e. g. aqueous ethyl alcohol or aqueous acetic acid. These compounds, by reason of their solubility in organic solvents, are also especially adapted for inclusion in solutions of cellulose acetate and similar materials which are to be extruded or cast to form fibres or films;
One important application of the invention is in the treatment of photographic prints'where application of a solution of a compound of the foregoing general formula has the effect of whitening the highlights of the print. Considerable effort has hitherto been directed to the produc--- tion of prints having brilliant highlights, and the present invention provides a simple method whereby this result may be achieved. However, the compounds may, if desired, be incorporated in the photographic emulsions, or sub-coat or supercoat layers, prior to coating such layers to form the photographic element.
cornpound. according to this invention the tone may be changed to resemble very closely the cold tone commonly associated with prints made on paper coated with silver chloride emulsions.
The compounds of this invention may also be applied to films coated on supports, for example to finished photographic films or plates where the gelatin film takes up the compound and is photographic thereby caused to fluoresce and the image to appear colder in tone. What we claim is:
1. A process 'for improving fibres and films which comprises applying thereto a dispersion in a liquid medium of a white fluorescent compound of the general formula:
" nic eflxr,
l klg wherein R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and Ara is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
2. A process for improving fibres and films which comprises applying thereto an aqueous solution of a white fluorescent compound of the general formula:
wherein R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and M2 is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
3. A process for improving fibres and films which comprises applying thereto an aqueous solution of a fluorescent compound of the general formula:
II N I An wherein R1 is selectedfrom the class consisting of the hydrogen atom, alkyl, unsubstituted 61' phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, ,Ar1 is selected from the class consisting of. unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy 1 and phenoxy substituents, and A12 is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl,-sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by'weight of the said compound.
5. A process for improving the whiteness of wool fibres and woollen textile materials which comprises applying thereto an aqueous solution of a compound of the general formula:
All
wherein R1 is a sulphonated phenyl group, An is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and
Arz is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
6. Thin flexible organic materials for use in textiles and photographic printing containing 0.01 to 1% of a white fluorescent compound of the general formula:
from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents.
'7. Woollen textile materials having adsorbed, thereto 0.01 to 1% of a white fluorescent com-' pound of the general formula:
I An
wherein R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and An is selected from the class, consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic andacetylamino substituents. i
8. Woollen textile materials having adsorbed,
7 thereto 0.01 to 1% of'a white fluorescent compound of the general formula H;C o-Ar, m-nc- N t Ara wherein R1 is a sulphonated phenyl group, Ar is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and A1: is selected from the'class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents.
9. Photographic light-sensitive materials having adsorbed thereto 0.01 to 1% by weight of a fluorescent compound of the general formula:
Ara wherein R1 is selected from the classconsisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, AT]. is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and 'Alz is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and acetylamino substituents.
10. Photographic printing paper having adsorbed thereto 0.01 to 1% by weight of a compound of the general formula:
wherein R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and Arz is selected from. the class consisting of unsubstituted phenyl and,
phenyl containing halogen, alkyl, sulphonic and acetylamino substitue'nts.
11. Process for improving the whiteness of the highlights of photographic prints on paper which comprises treating the prints with a dilute solution of a compound of the formula:
H3C C-Afl wherein R1 is selected from the class consisting of the hydrogen atom, alkyl, unsubstituted phenyl and phenyl containing alkyl, alkoxy, chloro and sulphonic substituents, Ari is selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, alkoxy and phenoxy substituents, and Ar: i selected from the class consisting of unsubstituted phenyl and phenyl containing halogen, alkyl, sulphonic and' acetylamino substituents, so that the said fibres 8 and films absorb 0.01 to 1% by weighto! the said compound.
12. A process for improving fibres and, films which comprises applying thereto a dispersion in a liquid medium of a white fluorescent compound of the general formula:
wherein R1 is selected from the class consisting of the hydrogen atom, methyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl and sulphophenyl groups, X1 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, methoxy, ethoxy and phenoxy, and X2 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, sulphonic and acetylamino groups, so that the said fibres and films absorb 0.01 to 1% by weight of the said compound.
13. Thin flexible organic materials for use in textiles and photographic printing containing 0.01 to 1% of a white fluorescent compound of the general formula:
wherein R1 is selected from the class consisting of the hydrogen atom, methyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl and sulphophenyl groups, X1 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, methoxy, ethoxy and phenoxy, and X2 represents at least one substituent group selected from the class consisting of hydrogen, halogen, methyl, sulphonic and acetylamino groups.
JOHN DAVID KENDALL. GEORGE FRANK DUFFIN.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,153,615 Dahlen et al Aug. 11, 1939 FOREIGN PATENTS Number Country Date 566,810 Great Britain Jan. 15, 1945 OTHER REFERENCES Beilstein (Vierte Auflauge-vol. 23- 168, citing Berichte 54 (1921), 1011 and Berichte 59 (1926) 611.
Samuels et al., Journal Society Dyers Colourists, August 1947, p. 266.
Richardson, Journal Society Dyers Colour- 'ists, September 1948, p. 315.
Claims (1)
- 9. PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS HAVING ADSORBED THERETO 0.01 TO 1% BY WEIGHT OF A FLUORESCENT COMPOUND OF THE GENERAL FORMULA:
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB15009/49A GB669590A (en) | 1949-06-03 | 1949-06-03 | Improvements in or relating to a process for improving the whiteness of colour materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US2639990A true US2639990A (en) | 1953-05-26 |
Family
ID=10051454
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US165116A Expired - Lifetime US2639990A (en) | 1949-06-03 | 1950-05-29 | Process for improving the whiteness or color of materials and products resulting therefrom |
Country Status (6)
Country | Link |
---|---|
US (1) | US2639990A (en) |
CH (2) | CH288169A (en) |
DE (1) | DE966411C (en) |
FR (1) | FR1021379A (en) |
GB (1) | GB669590A (en) |
NL (1) | NL79254C (en) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2785133A (en) * | 1954-03-26 | 1957-03-12 | Gen Aniline & Film Corp | Compositions for a method of whitening fine fabrics |
US2837485A (en) * | 1958-06-03 | Ari-ch | ||
US2938292A (en) * | 1955-08-18 | 1960-05-31 | Ultra Violet Products Inc | Fingerprinting system |
US2983604A (en) * | 1955-11-03 | 1961-05-09 | Gen Aniline & Film Corp | Quenching solution for fluorescent photographic paper employed in the manufacture ofhalftone negatives |
US2985593A (en) * | 1958-09-26 | 1961-05-23 | Borden Co | Scintillator composition |
US3127266A (en) * | 1958-08-09 | 1964-03-31 | Chzxn | |
US3131079A (en) * | 1960-08-12 | 1964-04-28 | Bayer Ag | Brightening of fiber material by coating with 1, 3-diaryl- and 1, 3, 5-triaryl pyrazoline derivatives |
US3133080A (en) * | 1964-05-12 | Optical whitening agents of the | ||
US3141879A (en) * | 1964-07-21 | Chj-chz | ||
US3181949A (en) * | 1958-06-02 | 1965-05-04 | Gevaert Photo Prod Nv | Light sensitive elements having optical bleaching compositions coated thereon |
US3181950A (en) * | 1957-06-06 | 1965-05-04 | Gevaert Photo Prod Nv | Method for optical bleaching of coated photosensitive papers and resultant product |
US3181948A (en) * | 1958-06-02 | 1965-05-04 | Gevaert Photo Prod Nv | Method for optical bleaching of coated papers and resultant product |
US3257204A (en) * | 1958-08-22 | 1966-06-21 | Azoplate Corp | Electrophotographic reproduction material |
US3257203A (en) * | 1958-08-20 | 1966-06-21 | Azoplate Corp | Electrophotographic reproduction material |
US3378389A (en) * | 1962-03-31 | 1968-04-16 | Bayer Ag | 1, 3-diphenyl pyrazolines and method for brightening synthetic material therewith |
US3434837A (en) * | 1964-06-05 | 1969-03-25 | Eastman Kodak Co | Photographic element |
US3447943A (en) * | 1964-09-02 | 1969-06-03 | Ici Ltd | Process for the whitening of polymeric materials |
US3498791A (en) * | 1965-10-27 | 1970-03-03 | Keuffel & Esser Co | Two-component diazotype material |
US3755352A (en) * | 1966-12-23 | 1973-08-28 | Ciba Geigy Corp | 1-(4{40 -methoxysulphonyl-phenyl)-3-(4{41 -chlorophenyl)-pyrazoline |
US3754964A (en) * | 1971-02-26 | 1973-08-28 | Ciba Geigy Corp | Process for the continuous optical brightening of acylated cellulose fibre material |
US4595458A (en) * | 1985-05-17 | 1986-06-17 | Olin Corporation | Process for using selected fatty acid adducts of a 1,2,4-triazole as sizing or waterproofing agents for cellulosic materials |
US5208251A (en) * | 1986-05-09 | 1993-05-04 | Warner-Lambert Company | Styryl pyrazoles, isoxazoles and analogs thereof having activity as 5-lipoxygenase inhibitors, pharmaceutical compositions and methods of use therefor |
EP0915370A1 (en) * | 1997-11-04 | 1999-05-12 | Konica Corporation | Silver halide light-sensitive photographic material |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1104483B (en) * | 1955-10-10 | 1961-04-13 | Bayer Ag | Whitening agents |
DE1157193B (en) * | 1957-10-30 | 1963-11-14 | Unilever Nv | Lightening of textiles |
DE1419329B1 (en) * | 1962-04-21 | 1970-01-15 | Hoechst Ag | 1,3-diaryl-delta-pyrazoline compounds and their use as whitening agents |
DE1469222B1 (en) * | 1964-09-25 | 1972-03-09 | Hoechst Ag | Pyrazoline derivatives and their preparation and use |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2153615A (en) * | 1936-10-23 | 1939-04-11 | Du Pont | 1-aryl-5-pyrazolone-3-carboxylic acids |
GB566810A (en) * | 1943-05-20 | 1945-01-15 | Unilever Ltd | Method of and preparations for improving the whiteness of materials |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR878823A (en) * | 1941-02-18 | 1943-02-04 | Ig Farbenindustrie Ag | Process for emphasizing whites and the luminous power of the surface color of photographic images |
DE735478C (en) * | 1941-07-12 | 1943-05-18 | Ig Farbenindustrie Ag | Process for the preparation of 4,5-Diarylimidazolineabkoemmlingen |
GB584435A (en) * | 1944-03-01 | 1947-01-15 | Unilever Ltd | Improvements in the laundering of white textile articles |
-
1949
- 1949-06-03 GB GB15009/49A patent/GB669590A/en not_active Expired
-
1950
- 1950-05-29 US US165116A patent/US2639990A/en not_active Expired - Lifetime
- 1950-05-30 NL NL153852A patent/NL79254C/xx active
- 1950-06-02 FR FR1021379D patent/FR1021379A/en not_active Expired
- 1950-06-03 DE DEI1016A patent/DE966411C/en not_active Expired
- 1950-06-03 CH CH288169D patent/CH288169A/en unknown
-
1952
- 1952-08-25 CH CH308746D patent/CH308746A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2153615A (en) * | 1936-10-23 | 1939-04-11 | Du Pont | 1-aryl-5-pyrazolone-3-carboxylic acids |
GB566810A (en) * | 1943-05-20 | 1945-01-15 | Unilever Ltd | Method of and preparations for improving the whiteness of materials |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2837485A (en) * | 1958-06-03 | Ari-ch | ||
US3133080A (en) * | 1964-05-12 | Optical whitening agents of the | ||
US3141879A (en) * | 1964-07-21 | Chj-chz | ||
US2785133A (en) * | 1954-03-26 | 1957-03-12 | Gen Aniline & Film Corp | Compositions for a method of whitening fine fabrics |
US2938292A (en) * | 1955-08-18 | 1960-05-31 | Ultra Violet Products Inc | Fingerprinting system |
US2983604A (en) * | 1955-11-03 | 1961-05-09 | Gen Aniline & Film Corp | Quenching solution for fluorescent photographic paper employed in the manufacture ofhalftone negatives |
US3181950A (en) * | 1957-06-06 | 1965-05-04 | Gevaert Photo Prod Nv | Method for optical bleaching of coated photosensitive papers and resultant product |
US3181949A (en) * | 1958-06-02 | 1965-05-04 | Gevaert Photo Prod Nv | Light sensitive elements having optical bleaching compositions coated thereon |
US3181948A (en) * | 1958-06-02 | 1965-05-04 | Gevaert Photo Prod Nv | Method for optical bleaching of coated papers and resultant product |
US3127266A (en) * | 1958-08-09 | 1964-03-31 | Chzxn | |
US3257203A (en) * | 1958-08-20 | 1966-06-21 | Azoplate Corp | Electrophotographic reproduction material |
US3257204A (en) * | 1958-08-22 | 1966-06-21 | Azoplate Corp | Electrophotographic reproduction material |
US2985593A (en) * | 1958-09-26 | 1961-05-23 | Borden Co | Scintillator composition |
US3131079A (en) * | 1960-08-12 | 1964-04-28 | Bayer Ag | Brightening of fiber material by coating with 1, 3-diaryl- and 1, 3, 5-triaryl pyrazoline derivatives |
US3378389A (en) * | 1962-03-31 | 1968-04-16 | Bayer Ag | 1, 3-diphenyl pyrazolines and method for brightening synthetic material therewith |
US3434837A (en) * | 1964-06-05 | 1969-03-25 | Eastman Kodak Co | Photographic element |
US3447943A (en) * | 1964-09-02 | 1969-06-03 | Ici Ltd | Process for the whitening of polymeric materials |
US3498791A (en) * | 1965-10-27 | 1970-03-03 | Keuffel & Esser Co | Two-component diazotype material |
US3755352A (en) * | 1966-12-23 | 1973-08-28 | Ciba Geigy Corp | 1-(4{40 -methoxysulphonyl-phenyl)-3-(4{41 -chlorophenyl)-pyrazoline |
US3754964A (en) * | 1971-02-26 | 1973-08-28 | Ciba Geigy Corp | Process for the continuous optical brightening of acylated cellulose fibre material |
US4595458A (en) * | 1985-05-17 | 1986-06-17 | Olin Corporation | Process for using selected fatty acid adducts of a 1,2,4-triazole as sizing or waterproofing agents for cellulosic materials |
US5208251A (en) * | 1986-05-09 | 1993-05-04 | Warner-Lambert Company | Styryl pyrazoles, isoxazoles and analogs thereof having activity as 5-lipoxygenase inhibitors, pharmaceutical compositions and methods of use therefor |
EP0915370A1 (en) * | 1997-11-04 | 1999-05-12 | Konica Corporation | Silver halide light-sensitive photographic material |
Also Published As
Publication number | Publication date |
---|---|
DE966411C (en) | 1957-08-01 |
CH288169A (en) | 1953-01-15 |
GB669590A (en) | 1952-04-02 |
NL79254C (en) | 1955-10-15 |
CH308746A (en) | 1955-07-31 |
FR1021379A (en) | 1953-02-18 |
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