US2489384A - Benzene-azo-benzene-azo-oleyl phenol - Google Patents

Benzene-azo-benzene-azo-oleyl phenol Download PDF

Info

Publication number
US2489384A
US2489384A US682294A US68229446A US2489384A US 2489384 A US2489384 A US 2489384A US 682294 A US682294 A US 682294A US 68229446 A US68229446 A US 68229446A US 2489384 A US2489384 A US 2489384A
Authority
US
United States
Prior art keywords
azo
phenol
benzene
coloured
oleyl
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 - Lifetime
Application number
US682294A
Inventor
Olpin Henry Charles
House Kenneth Ronald
Wright John
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.)
Celanese Corp
Original Assignee
Celanese Corp
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
Priority claimed from GB1862645A external-priority patent/GB599278A/en
Application filed by Celanese Corp filed Critical Celanese Corp
Application granted granted Critical
Publication of US2489384A publication Critical patent/US2489384A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/062—Phenols
    • 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

Definitions

  • This invention relates to the production of coloured fibres, foils, films or the like of cellulose.
  • 2,393,652 describe the spinning of coloured fibres from solutions of fibre-forming materials;- the said solutions being coloured with a dye having therein a mono-valent aliphatic radicle free from sulphonic acid carboxylic groups, the said-"aliphatic radicle containing at least 8 carbonatoms united by carbon to carbon linkages, and-particularly a mono-valent aliphatic hydrocarbon radicle containing at least 8 carbon atoms.
  • the dyes are free from sulphonicand carboxylic groups. In this way it is possible to obtain coloured fibres which are very resistant to loss of colour when subjected to washing.
  • coloured fibres can be produced which are bright in shade and lack the undesirable greasy appearance which so often characterises fibres spun from solutions coloured with pigment's.
  • the latter feature seems to be due to the fact that the dye is largely or wholly insolution in the spinning solution and not merely suspended therein as in the case of a pigment. Solubility of the dye in the spinning solution is also of great advantage from the point of I'v'iew of preparing homogeneous spinning solutions containing a definite and predetermined proportion of dye. Moreover when the dye is in 'solution the spinning solution is not likely to lose a dye, as does a solution containing a pigment,
  • dyes of this type are as a class yellow; and have very good solubility in organic liquids, notably acetone; so greatly facilitating the preparation of coloured spinning solutions.
  • cellulose acetate and other fibres coloured with the dyes are very resistant to removal of the dye by washing and like hot aqueous treatments.
  • the aliphatic radicles are preferably hydrocarbon radicles and maybe saturated or unsaturated and may comprise either a straight chain of carbon atoms or a branched chain of carbon atoms... Again the aliphatic radicles may be either primary, secondary, or tertiary, that is the carbon atom thereof at which the radicle is attached to thephenol nucleus may be directly attached to one, two, or three other carbon atoms of the aliphatic radicle. It is advantageous that the. aliphatic radicle. should contain :a chain of at least 6 or 8 carbon atoms counting from and including the carbon atom at which the. radicle .is attached to the phenol nucleus.
  • phenols whichmay be used in :;the preparation of the dyes may be'mentioned .the'alkyl phenols obtainable by heating a phenol, for example phenol itself or a cresol, e. g. m-cresol, or a hydroxydiphenyl with an aliphatic alcohol "containing at -least.9 carbon atoms in the pres ence of zincchloride.
  • a phenol for example phenol itself or a cresol, e. g. m-cresol, or a hydroxydiphenyl
  • an aliphatic alcohol "containing at -least.9 carbon atoms in the pres ence of zincchloride e. g. m-cresol
  • thealiphatic radicle is situated in para position to the OH group if the para position of the parent phenol is free. Otherwise it is in ortho-position to. the OH group.
  • the aliphatic alcohol can be for-instance dodecyl alcohol, hexadecyl alcohol, :octadecyl alcohol or oleyl alcohol or mixtures .-;0f two or moreof these alcohols.
  • oleyl alcohol is meant the alcohol corresponding with oleic acid and diifering therefrom in having a CHzOH group in place'of the COOH group.
  • the alkyl phenols obtainable by heating phenols with oleyl alcohol in the presence of zinc chloride are hereinafter referred to as oleyl phenols, and the .:unsaturated hydrocarbon radicle so introduced into the phenol molecule is referred to as the oleyl radicle.
  • phenols which may be employed are the nuclear acidyl phenols in which the acidyl radicle is that of an aliphatic carboxylic acid containing a substantial number of carbon-atoms, for example at least 9, e. g. lauric acid, palmitic acid, or stearic acid.
  • p-Lauroyl phenol is an example of such a phenol.
  • the diazo compounds used for the production of the dyes can be those of aniline, chloranilines,
  • an arylamide or other amide of p-amino-benzoic acid can be used, e. g.
  • Our invention includes the; .dyes and processes .for their manufacture, as'wellas fibresfoils, films,
  • fibres may be producedybyspinning.the solutions ;either into; suitable. evaporative atmospheres. or :intorsuitable coagulation baths.
  • the :fibres.. may of course .be. assembled into tyarns. at the. time of .fsp-inningl .as is commonly practised.
  • .Againthefibres maybe cutinto staple .gfibre. and this, either.- aloneor mixedwith.
  • other textile fibres e. g. wool, silk, cotton, or regenerated cellulose, fibres, converted into yarn by the methods commonly employed for converting .cottonor wool into yarns.
  • .Yarns. consisting 40f .or .containingthe: coloured: fibres of :the invention can be formed into fabrics byweaving'or knitting.
  • the invention may; subsequently be. topped with other dyes and particularlywith' direct-dye- .ing. dyes for celluloseesters or, ethers, for. example .the water-insoluble; dyestuffs .oflthe” nitrodiarylamine, azo, or .ami-no-anthraquinone :series, such as are extensively employed for the colouratlon of cellulose acetate materials.
  • the topping colouring matter may be applied either uniformly or locally according to the effects it is desired to produce.
  • the topping colours may be applied, for instance, in aqueous solution or dispersion according to their nature, or in solution in organic solvents.
  • a single coloured material produced in accordance with the invention can thus be utilised .to yield..a,.range..of materials of..difierent
  • organic liquid media can be those referred to in U. S.
  • Patent No. 2,384,001 in connection with the employment of arylamino-anthraquinones for colcuring cellulose ester or ether materials. Again the dye liquids can be applied to the materials 1 in any-of the waysdescribed in U. S. Patent No. 2,384,001.
  • the invention isof especial value in the .pro-' .duction of coloured cellulose. acetate fibre, foils,
  • Similar. coloured products of other fibre-forming materials soluble-in organic liquids, particularly other cellulose esters or ethers, can be obtainedlikewise, for example-of cellulosepropionate, -butyrate,. aceto-propionate, aceto-butyrate, .nitroacetate, and of methyl ethyl and benzyl celluloses, andfibres and otherproductsof polymerised vinyl compounds.
  • ar'id lOO parts-of zinc' chloride are refluxed together for 16 hours.
  • the product is washed with solubility in acetone cellulose acetatemrother e 500*partsof 10% hydrochloric acid, then "with 'water, then with caustic soda'solution, and again with water.
  • Example II -10.6--par-ts -of-' p-benzoylamino-aniline (monobenzoyl-p-phenylene diamine) are dissolvedin 90 g The coloured materials .producedin. accordance parts of hotmethylated spirit; 25 parts of 2N'sodium nitrite'added and the whole poured into'a anhydrous zinc chloride for 6 hours.
  • Cellulose acetate filaments are then dry spun from a 25% acetone solution of cellulose acetate containing 1.5% of the dye based on the weight of the cellulose acetate. Filaments are obtained which are of a golden yellow shade very resistant to hot soaping treatments.
  • Example III 30 parts of secondary dodecyl alcohol are heated with 38 parts of phenol and 38 parts of After washing well with dilute hydrochloric acid and water the resulting p-sec.-dodecyl phenol is separated from residual phenol by vacuum distillation, the phenol distilling first.
  • the sec.-dodecyl phenol is then coupled with an equi-molecular proportion of diazotised aminoazobenzene in dilute methylated spirit and in presence of sodium carbonate.
  • the product is extremely soluble in acetone.
  • the p-sec.-dodecyl phenol can similarly be coupled with diazotised p-amino-acetanilide and p-amino-benzanilide.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)

Description

Patented Nov. 29, 1949 BENZENE-AZO-BENZENE-AZO;0LEYL I PHENOL Henry Charles Olpin, Kenneth Ronald House, and John Wright, Spondon, near Derby, England,
assignors to Ceianese Corporation of America, a corporation of Delaware No Drawing. Application July 9, 1946, Serial No. I 682,294. In Great Britain July 20, 1945 1 Claim. 1
This invention relates to the production of coloured fibres, foils, films or the like of cellulose.
acetate or other cellulose esters-or ethers' or of other fibreor film-forming materials which are soluble in organic liquids.
U. S. Patent No. 2,420,008 and U. S. PatentNo.
2,393,652 describe the spinning of coloured fibres from solutions of fibre-forming materials;- the said solutions being coloured with a dye having therein a mono-valent aliphatic radicle free from sulphonic acid carboxylic groups, the said-"aliphatic radicle containing at least 8 carbonatoms united by carbon to carbon linkages, and-particularly a mono-valent aliphatic hydrocarbon radicle containing at least 8 carbon atoms. -l3referably the dyes are free from sulphonicand carboxylic groups. In this way it is possible to obtain coloured fibres which are very resistant to loss of colour when subjected to washing. Further, coloured fibres can be produced which are bright in shade and lack the undesirable greasy appearance which so often characterises fibres spun from solutions coloured with pigment's. The latter feature seems to be due to the fact that the dye is largely or wholly insolution in the spinning solution and not merely suspended therein as in the case of a pigment. Solubility of the dye in the spinning solution is also of great advantage from the point of I'v'iew of preparing homogeneous spinning solutions containing a definite and predetermined proportion of dye. Moreover when the dye is in 'solution the spinning solution is not likely to lose a dye, as does a solution containing a pigment,
on passage through the filters which must usually precede the spinning nozzles.
' We have found that the production of coloured (particularly yellow) fibres, foils, films or the like of cellulose acetate or other cellulose esters or ethers, or other fibreor film-forming materials soluble in organic liquids can very advantageously be efiected with the aid of azo dyes obtainable by coupling diazo compounds with phenols having as nuclear substituents aliphatic radicles containing at least '8 carbon atoms, but preferably at least 12 carbon atoms, united by carbon to carbon linkages. The aliphatic radicles should be free from sulphonic and carboxylic groups. These dyes can be regarded as hydroxy aryl-azo-aryl compounds having the aliphatic radicle inquestion as a substituent in the aryl nucleus carrying the hydroxyl group.
-We have found that dyes of this type are as a class yellow; and have very good solubility in organic liquids, notably acetone; so greatly facilitating the preparation of coloured spinning solutions. Moreover cellulose acetate and other fibres coloured with the dyes are very resistant to removal of the dye by washing and like hot aqueous treatments.
The aliphatic radicles are preferably hydrocarbon radicles and maybe saturated or unsaturated and may comprise either a straight chain of carbon atoms or a branched chain of carbon atoms... Again the aliphatic radicles may be either primary, secondary, or tertiary, that is the carbon atom thereof at which the radicle is attached to thephenol nucleus may be directly attached to one, two, or three other carbon atoms of the aliphatic radicle. It is advantageous that the. aliphatic radicle. should contain :a chain of at least 6 or 8 carbon atoms counting from and including the carbon atom at which the. radicle .is attached to the phenol nucleus. In general the presence of an unsaturated radicle such as the oleyl radicle Clams-leads to a dye .which is considerably more soluble in acetone .than is the dye containing. the corresponding saturated aliphatic radicle.
Asexamples of phenols whichmay be used in :;the preparation of the dyes may be'mentioned .the'alkyl phenols obtainable by heating a phenol, for example phenol itself or a cresol, e. g. m-cresol, or a hydroxydiphenyl with an aliphatic alcohol "containing at -least.9 carbon atoms in the pres ence of zincchloride. In these particular phenols thealiphatic radicle is situated in para position to the OH group if the para position of the parent phenol is free. Otherwise it is in ortho-position to. the OH group. The aliphatic alcohol can be for-instance dodecyl alcohol, hexadecyl alcohol, :octadecyl alcohol or oleyl alcohol or mixtures .-;0f two or moreof these alcohols. By oleyl alcohol is meant the alcohol corresponding with oleic acid and diifering therefrom in having a CHzOH group in place'of the COOH group. The alkyl phenols obtainable by heating phenols with oleyl alcohol in the presence of zinc chloride are hereinafter referred to as oleyl phenols, and the .:unsaturated hydrocarbon radicle so introduced into the phenol molecule is referred to as the oleyl radicle. Another class of phenols which may be employed are the nuclear acidyl phenols in which the acidyl radicle is that of an aliphatic carboxylic acid containing a substantial number of carbon-atoms, for example at least 9, e. g. lauric acid, palmitic acid, or stearic acid. p-Lauroyl phenol is an example of such a phenol.
The diazo compounds used for the production of the dyes can be those of aniline, chloranilines,
exsh'ades.
toluidines, xylidines; anisidines, or p-acidylamino anilines; e. g. p-acetylamino-aniline or p-benzoylamino-aniline. Again an arylamide or other amide of p-amino-benzoic acid can be used, e. g.
the anilide of p-amino-benzoic ac'id. Further ..zinc. chloride, or the cetylp-hydroxydiphenyl obtainable by heating.-p-hydroxydiphenyl with .cetyl alcohol in presence of-zinc chloride .or the .oleylphenol obtainable by heating phenol with oleyl alcohol in presence of .zinczchloride. All these dyes are yellow in shade.
Our invention includes the; .dyes and processes .for their manufacture, as'wellas fibresfoils, films,
or. :the like, coloured therewith.
The proportions in which vzthe -::dyes are. :em-
forming material. Owing -.:to the very '..high
.zfibres or;..pr0ducts. containing. very high-.proportions of the dyes canbenproduced viaacetone solutions of the cellulose. acetateor other materials in which the whole of the requisite. dye is: in solution -rather.;than in suspension.
,jiEither wet ordry.methods may be used -for :spinning intolfibreswthe solutionsof the fibre- .formingxmaterials containing :the dyes; thus fibres may be producedybyspinning.the solutions ;either into; suitable. evaporative atmospheres. or :intorsuitable coagulation baths. The invention-is .of special value in connection with'the production of: coloured cellulose, acetate fibres by. the; spinning of acetone solutions of cellulose. acetate.
The :fibres..may of course .be. assembled into tyarns. at the. time of .fsp-inningl .as is commonly practised. .Againthefibres maybe cutinto staple .gfibre. and this, either.- aloneor mixedwith. other textile fibres, e. g. wool, silk, cotton, or regenerated cellulose, fibres, converted into yarn by the methods commonly employed for converting .cottonor wool into yarns. .Yarns. consisting 40f .or .containingthe: coloured: fibres of :the invention can be formed into fabrics byweaving'or knitting.
:with the invention may; subsequently be. topped with other dyes and particularlywith' direct-dye- .ing. dyes for celluloseesters or, ethers, for. example .the water-insoluble; dyestuffs .oflthe" nitrodiarylamine, azo, or .ami-no-anthraquinone :series, such as are extensively employed for the colouratlon of cellulose acetate materials. The topping colouring matter may be applied either uniformly or locally according to the effects it is desired to produce. The topping colours may be applied, for instance, in aqueous solution or dispersion according to their nature, or in solution in organic solvents. A single coloured material produced in accordance with the invention can thus be utilised .to yield..a,.range..of materials of..difierent The dyes of the present invention, like those of U. S. Patent No. 2,420,008, and U. S. Patent No. 2,393,652, have as a class little or no afiinity for fibres of cellulose esters or ethers or other fibreforming materials when applied thereto in the ordinary way as aqueous dispersions. It has been .iound, however, that valuable colourations can .=be obtained-Joy applying the dyes in the form of free from sulphonic,.-- t
solutions. inorganic liquid media. The organic liquid media can be those referred to in U. S.
"Patent No. 2,384,001 in connection with the employment of arylamino-anthraquinones for colcuring cellulose ester or ether materials. Again the dye liquids can be applied to the materials 1 in any-of the waysdescribed in U. S. Patent No. 2,384,001.
The invention isof especial value in the .pro-' .duction of coloured cellulose. acetate fibre, foils,
films, and the like. Similar. coloured products of other fibre-forming materials soluble-in organic liquids, particularly other cellulose esters or ethers, can be obtainedlikewise, for example-of cellulosepropionate, -butyrate,. aceto-propionate, aceto-butyrate, .nitroacetate, and of methyl ethyl and benzyl celluloses, andfibres and otherproductsof polymerised vinyl compounds.
. Theinventionis illustrated by the-following. ex-
amples, the parts referred to being parts by ",ployed in the production of coloured-:fibres, foils, 40 films orthe like can be within' widelimits, .for ex- ,ample from 0.5.to 2.5 per centbasedon the weight 0f: the cellulose acetate or other: fibre-.or-filmweight:
Trample I 100 partsof oleyl alcohol, 100 partsof phenol,
ar'id lOO parts-of zinc' chloride are refluxed together for 16 hours. The product is washed with solubility in acetone cellulose acetatemrother e 500*partsof 10% hydrochloric acid, then "with 'water, then with caustic soda'solution, and again with water.
parts of methylatedspirit. -chloric acid of 32% strength, 100 parts of ice and 10 parts of amino-azo-benzene isstirred into'90 '17 parts of hydro- 25" parts of 2N-sodium nitrite solution are then added. The diazo solution so prepared is then 'fil'ter'ed into a solution of 17 parts of the oleyl soluble in acetone.
.from a 25%, solution of cellulose acetate in acetone containing 1.5% 'oflthe dye based onithe weight of'the cellulose acetate. "filaments which are non-'phototropic and are of Golden yellow go'od-fastness'to' scouring are obtained.
Example II -10.6--par-ts -of-' p-benzoylamino-aniline (monobenzoyl-p-phenylene diamine) are dissolvedin 90 g The coloured materials .producedin. accordance parts of hotmethylated spirit; 25 parts of 2N'sodium nitrite'added and the whole poured into'a anhydrous zinc chloride for 6 hours.
Cellulose acetate filaments are then dry spun from a 25% acetone solution of cellulose acetate containing 1.5% of the dye based on the weight of the cellulose acetate. Filaments are obtained which are of a golden yellow shade very resistant to hot soaping treatments.
Example III 30 parts of secondary dodecyl alcohol are heated with 38 parts of phenol and 38 parts of After washing well with dilute hydrochloric acid and water the resulting p-sec.-dodecyl phenol is separated from residual phenol by vacuum distillation, the phenol distilling first.
The sec.-dodecyl phenol is then coupled with an equi-molecular proportion of diazotised aminoazobenzene in dilute methylated spirit and in presence of sodium carbonate. The product is extremely soluble in acetone. By spinning an acetone solution of cellulose acetate containing 1.5% of the dye on the weight of the cellulose acetate, golden yellow fibres of very good fastness to soap scouring are obtained.
The p-sec.-dodecyl phenol can similarly be coupled with diazotised p-amino-acetanilide and p-amino-benzanilide.
6 Having described our invention, what we desire to secure by Letters Patent is:
Benzene-azo-benzene-azo-oleyl phenol.
HENRY CHARLES OLPIN. KENNETH RONALD HOUSE. JOHN WRIGHT.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 902,021 Sulzberger Oct. 27, 1908 2,034,668 Reindel et al Mar. 17, 1936 2,072,252 Ellis Mar. 2, 1937 2,083,308 Senn June 8, 1937 2,126,841 Thurm Aug. 16, 1938 2,127,478 Crosley et a1 Aug. 16, 1938 2,158,283 Haddock et a1 May 16, 1939 2,196,985 Flett Apr. 16, 1940 2,266,413 Crossley Dec. 16, 1941 2,286,317 Stanley June 16, 1942 2,302,530 Crossley Nov. 17, 1942 2,315,232 Thurm et a1. Mar. 30, 1943 2,393,652 Olpin et a1 Jan. 29, 1946 2,402,538 Dreyfus June 25, 1946 FOREIGN PATENTS Number Country Date 791,902 France Oct. 7, 1935 558,330 Great Britain Dec.- 31, 1943
US682294A 1945-07-20 1946-07-09 Benzene-azo-benzene-azo-oleyl phenol Expired - Lifetime US2489384A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1862645A GB599278A (en) 1945-07-20 Improvements in dyes and in coloured fibres, foils and films

Publications (1)

Publication Number Publication Date
US2489384A true US2489384A (en) 1949-11-29

Family

ID=10115688

Family Applications (1)

Application Number Title Priority Date Filing Date
US682294A Expired - Lifetime US2489384A (en) 1945-07-20 1946-07-09 Benzene-azo-benzene-azo-oleyl phenol

Country Status (1)

Country Link
US (1) US2489384A (en)

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US902021A (en) * 1907-10-02 1908-10-27 Nathan Sulzberger Process of making azo dyes containing fatty acid radicals.
FR791902A (en) * 1934-06-28 1935-12-19 Ici Ltd Synthetic dyes and their manufacturing processes
US2034668A (en) * 1931-03-26 1936-03-17 Gen Aniline Works Inc Azo dyestuffs
US2072252A (en) * 1932-03-12 1937-03-02 Celanese Corp Coloring textile material
US2083308A (en) * 1935-08-27 1937-06-08 Firm Of J R Geigy A G Monoazo-dyestuffs and their manufacture
US2127478A (en) * 1937-03-23 1938-08-16 Calco Chemical Co Inc Orange disazo dyes
US2126841A (en) * 1934-05-26 1938-08-16 Gen Aniline Works Inc Azo dyestuffs and their production
US2158283A (en) * 1935-06-25 1939-05-16 Ici Ltd Dyestuffs
US2196985A (en) * 1934-07-31 1940-04-16 Nat Aniline & Chem Co Inc Alkyl hydroxy aromatic sulphonates
US2266413A (en) * 1937-03-29 1941-12-16 American Cyanamid Co Azo dyes
US2286317A (en) * 1938-12-30 1942-06-16 Celanese Corp Dye
US2302530A (en) * 1937-03-29 1942-11-17 American Cyanamid Co Azo dye
US2315232A (en) * 1936-03-31 1943-03-30 Gen Aniline & Film Corp Water-insoluble disazo dyes
GB558330A (en) * 1942-06-29 1943-12-31 Basil Jason Heywood Manufacture of new monoazo dyestuffs
US2393652A (en) * 1941-07-25 1946-01-29 British Celanese Production of colored textile and other materials
US2402538A (en) * 1940-06-03 1946-06-25 Celanese Corp Manufacture of coloring matters

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US902021A (en) * 1907-10-02 1908-10-27 Nathan Sulzberger Process of making azo dyes containing fatty acid radicals.
US2034668A (en) * 1931-03-26 1936-03-17 Gen Aniline Works Inc Azo dyestuffs
US2072252A (en) * 1932-03-12 1937-03-02 Celanese Corp Coloring textile material
US2126841A (en) * 1934-05-26 1938-08-16 Gen Aniline Works Inc Azo dyestuffs and their production
FR791902A (en) * 1934-06-28 1935-12-19 Ici Ltd Synthetic dyes and their manufacturing processes
US2196985A (en) * 1934-07-31 1940-04-16 Nat Aniline & Chem Co Inc Alkyl hydroxy aromatic sulphonates
US2158283A (en) * 1935-06-25 1939-05-16 Ici Ltd Dyestuffs
US2083308A (en) * 1935-08-27 1937-06-08 Firm Of J R Geigy A G Monoazo-dyestuffs and their manufacture
US2315232A (en) * 1936-03-31 1943-03-30 Gen Aniline & Film Corp Water-insoluble disazo dyes
US2127478A (en) * 1937-03-23 1938-08-16 Calco Chemical Co Inc Orange disazo dyes
US2266413A (en) * 1937-03-29 1941-12-16 American Cyanamid Co Azo dyes
US2302530A (en) * 1937-03-29 1942-11-17 American Cyanamid Co Azo dye
US2286317A (en) * 1938-12-30 1942-06-16 Celanese Corp Dye
US2402538A (en) * 1940-06-03 1946-06-25 Celanese Corp Manufacture of coloring matters
US2393652A (en) * 1941-07-25 1946-01-29 British Celanese Production of colored textile and other materials
GB558330A (en) * 1942-06-29 1943-12-31 Basil Jason Heywood Manufacture of new monoazo dyestuffs

Similar Documents

Publication Publication Date Title
US2083122A (en) Manufacture of artificial filaments, threads, films, and the like
US2393652A (en) Production of colored textile and other materials
US2489384A (en) Benzene-azo-benzene-azo-oleyl phenol
US2017119A (en) Treatment of textile and other materials
US2206278A (en) Textile and other materials
US2072252A (en) Coloring textile material
US2563091A (en) Dyes
US2559787A (en) Colored cellulose esters and ethers
US2289414A (en) Azo dye and coloration of cellulose derivatives therewith
US2053276A (en) Coloration of textile material
US1534019A (en) Dyeing acetyl cellulose or fabrics containing the same and new products for use therein
US2899421A (en) Monoazo-dyestuffs insoluble in water
US2048796A (en) Treatment of textile materials
US2286317A (en) Dye
US2053274A (en) Production and use of dyestuffs
US2412312A (en) Cellulose acetate dyed with monoazo dyes
US3445485A (en) 1-amino-2 methylolcyclo-hexylmethoxy-4-hydroxy-anthraquinones
US2010884A (en) Coloration of materials
US1935657A (en) Manufacture of new dyestuffs and the application thereof
US1871673A (en) Coloring of cellulose derivatives
US1892480A (en) Azo-dyestuffs
US2048786A (en) Treatment of textile material
US2464885A (en) Cellulose ester and ether products colored with a dinitro-phenoxazine or -phenthiazine
US2094770A (en) Dyeing of organic derivatives of cellulose
US2132456A (en) Dyeing cellulose esters and ethers