US2255090A - Inhibiting the gas fading of dyed acetate silk - Google Patents
Inhibiting the gas fading of dyed acetate silk Download PDFInfo
- Publication number
- US2255090A US2255090A US318706A US31870640A US2255090A US 2255090 A US2255090 A US 2255090A US 318706 A US318706 A US 318706A US 31870640 A US31870640 A US 31870640A US 2255090 A US2255090 A US 2255090A
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- United States
- Prior art keywords
- amino
- dyed
- fibers
- biguanide
- inhibiting
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/20—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylguanidines
- C07C279/24—Y being a hetero atom
- C07C279/26—X and Y being nitrogen atoms, i.e. biguanides
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6494—Compounds containing a guanyl group R-C-N=, e.g. (bi)guanadine, dicyandiamid amidines
Definitions
- This invention relates to improvements in dyed cellulose acetate fibers, and especially to the prevention of fading which results when such dyed fibers are exposed to deleterious fumes, such as atmosphere which contains oxides of nitrogen or sulfur.
- Another object of the invention is to provide means to inhibit the action of such deleterious gases on dyed cellulose acetate fibers. Another object of the invention is to provide inhibitors which do not deleteriously affect the shade and fastness of the dyes and which will give effective protection after the goods are cleaned. Other objects of the invention will be apparent from the following description.
- the objects of the invention are attained in general by afiixing to the fibers certain biguanides. These may be conveniently applied or affixed to the fibers by wetting or saturating the dyed fibers with a water solution or suspension of the inhibitor and then removing the water.
- Example I One-half to two parts of phenyl biguanide were dissolved in 100 parts of water by gentle warming and stirring. Five parts of cellulose acetate silk which had been dyed with 1,4- di(mono methyl amino) anthraquinone were immersed for a period of from 30 seconds to three minutes in the solution of phenyl biguanide. The solution temperature was between 25 and 100 C. The acetate rayon was removed and dried.
- Example II One part of phenyl biguanide was intimately mixed into a water solution containing one-half part of soap. Five parts of cellulose acetate silk dyed with 1,4,5,8-tetra-amino anthraquinone were entered and saturated in the dispersion which was held at 70 C. After five minutes, the saturated material was removed, rinsed and dried. Upon exposure to an atmosphere containing oxides of nitrogen, it remained unchanged while an untreated dyeing of the same kind faded to a considerable extent.
- Example III Cellulose acetate fabrics dyed with the azo dye represented by the formula were severally treated with phenyl biguanide and ortho tolyl biguanide similarly to the treatment described in Example I and similar protection from gases containing oxides'of nitrogen and sulfur was obtained.
- biguanides can be used in accordance with the invention and with the effect described in the foregoing examples.
- biguanides sometimes called blguanidines .o'r guanyl guanidines may be readily prepared by reacting a primary or secondary amine with dicyan diamide in the manner described in Jour. fi;:. prakt. Chem., 84, 396, thereby producing biguanides of the general formula 1 m H wherein R is hydrogen or the substituted group of the secondary amine.
- Mono-, bisor -trisbiguanides are produced when one, two or three groups are present in the nucleus. Accordingly aniline produces all of which have the described effect of the biguanides mentioned in the foregoing examples.
- amines are mentioned as the starting materials from which such representative biguanides are made; aniline, o, m and p-toluidines, xylidines, cresidine, 2,5-dimethoxy aniline, monoand di-chlor anilines, o, m and p-cyano aniline, m-amino benz'otrifluoride, 0, m and pamino phenyl methyl sulfone, o, m and p amino acetophenone, p-amino phenyl .beta-hydroxy ethyl ether, 0, m and p-anisidine and phenetidine, p-dodeoyl aniline, p-amino ethyl benzoate, sulfanilamide, p
- any of these nuclei may be unsubstituted or substituted once to twice by any combination of alkyl groups having 1 to 12 carbons, methoxy, ethoxy, CFa, halogen, COCH3, CN, acetylamino, -SO2CH3 and SO2 phenyl.
- the diphenyl compounds can be substituted in each benzene ring.
- m is 1 to 3 and R is one of a group consisting of hydrogen, alkyl having 1 to 5 carbons and hydroxyalkyl havingl to 5 carbons.
- the biguanides of the benzene series arethe preferred embodiments, such as those represented by the formula wherein A represents the nuclear substituents heretofore recited and n is 1 or 2, and of these the mono-biguanides are preferred.
- the biguanides used in carrying out the invention have good afiinity for cellulose acetate fibers resulting in rapid absorption and good retention by the fiber, but the precise reasons for their inhibiting action are not fully understood. It has been suggested that the inhibiting effect may be due to the formation of salts or oxides by the action of the deleterious fumes on the biguanides in preference to a salt forming or oxidizing action on the dye.
- the nature of the reaction products is not fully known and it is to be understood that the invention is not limited by the proposed theory.
- the invention is especially useful in improving the properties of dyed cellulose acetate fibers which are dyed with the anthraquinone and the monazo dyes, such as 1,4 di[mono hydroxy ethyl amino] anthraquinone, l-methyl amino-a-hydroxy ethyl amino anthraquinone, l-amino-4- methyl amino anthraquinone, 1,4-diamino-5- nitro anthraquinone, l-amino-4-anilidoanthra quinone and 4-amino-4-nitro-azobenzene with which a similar degree of protection is afforded by the biguanides described.
- the monazo dyes such as 1,4 di[mono hydroxy ethyl amino] anthraquinone, l-methyl amino-a-hydroxy ethyl amino anthraquinone, l-amino-4- methyl amino anthraquinone, 1,4-
- the biguanides it is commonly preferable to apply the biguanides as an after treatment to the dyed fiber but it may be applied during the dyeing operation by adding the inhibiting compound to the dyebath or other treating bath.
- Any manner of aifixing or adsorbing the inhibitor on and in the fiber gives beneficial results.
- a short immersion of the fibers, such as about thirty secends is frequently sufficient to give adequate protection but better results are sometimes obtained with longer immersions, such as three to five minutes.
- the adsorption of the inhibitor varies somewhat with the various circumstances but it is generally quite rapid. Considerably longer immersions than those mentioned can be employed when they are desired since they are not harmful, but such excessively long immersions are commonly unnecessary.
- the best duration of time for immersing the fibers may vary somewhat depending on circumstances, such as the particular inhibitor used, the character and condition of the fiber acter of the treating'bath.
- the wide variation permissible in the treatment is adanta eous since it lends itself desirably to the special circumstances encountered in practice.
- the fastness of the dyeings is not adversely affected and in most cases it is improved.
- a dyed article of cellulose acetate fibers which has affixed to said fibers phenyl biguanide.
- a dyed article of cellulose acetate fibers which has aifixed to said fibers phenyl ethyl biguanide.
- R is a nucleus of the benzene, naphthalene, heterocyclic and do.
- m is i to 3;
- R is one of a group consisting of hydrogen, alkyl having 1 to 5 carbons, hydroxyalkyl having 1 .to 5 carbons;
- A is from the group consisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy, CFc, halogen, COOCI-Is, CN, acetylamino, SOzCHa and -SO2 phenyl;
- n is an integer not greater than 2;
- p is an integer not greater than 2.
Description
Patented Sept. 9, 1941 mmnrrma 'rrm GAS FADING F DYED ACETATE smx John M. Tinker and Donovan E. Kvalnes, Perms Grove, N. J., assignors to E. L du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 13, 1940, Serial No. 318,706
7 Claims.
This invention relates to improvements in dyed cellulose acetate fibers, and especially to the prevention of fading which results when such dyed fibers are exposed to deleterious fumes, such as atmosphere which contains oxides of nitrogen or sulfur.
When dyed articles of cellulose acetate fibers are stored where they are exposed to atmosphere containing oxides of nitrogen and sulfur it has been observed that the dyeings change shade and lose strength. Fading is produced more or less rapidly by the action of various concentrations of the deleterious gases. Even in minute concentration, the deleterious gases are effective, as for example where the dyed goods are stored or exposed for a considerable period of time to an atmosphere which contains such small amounts of the deleterious oxides. It is therefore desirable to provide dyed cellulose acetate fibers so that they will have good fastness to dry cleaning and washing and will resist the action of deleterious gases. Means for such purposes are desired which will not have a harmful effect on the shade or fastness properties of the dyes.
It is among the objects of the invention to provide means to inhibit the action of such deleterious gases on dyed cellulose acetate fibers. Another object of the invention is to provide inhibitors which do not deleteriously affect the shade and fastness of the dyes and which will give effective protection after the goods are cleaned. Other objects of the invention will be apparent from the following description.
The objects of the invention are attained in general by afiixing to the fibers certain biguanides. These may be conveniently applied or affixed to the fibers by wetting or saturating the dyed fibers with a water solution or suspension of the inhibitor and then removing the water.
The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and not as limitations thereof. Parts are expressed in parts by weight unless otherwise noted.
Example I One-half to two parts of phenyl biguanide were dissolved in 100 parts of water by gentle warming and stirring. Five parts of cellulose acetate silk which had been dyed with 1,4- di(mono methyl amino) anthraquinone were immersed for a period of from 30 seconds to three minutes in the solution of phenyl biguanide. The solution temperature was between 25 and 100 C. The acetate rayon was removed and dried.
On exposure to the fumes of a gas burner and to atmosphere containing oxides of nitrogen, the
larly treated with ortho tolyl biguanide, like results were produced.
Example II One part of phenyl biguanide was intimately mixed into a water solution containing one-half part of soap. Five parts of cellulose acetate silk dyed with 1,4,5,8-tetra-amino anthraquinone were entered and saturated in the dispersion which was held at 70 C. After five minutes, the saturated material was removed, rinsed and dried. Upon exposure to an atmosphere containing oxides of nitrogen, it remained unchanged while an untreated dyeing of the same kind faded to a considerable extent.
Similar results were obtained by using phenyl, ethyl biguanide in suspension instead of phenyl bi uanide.
Example III Cellulose acetate fabrics dyed with the azo dye represented by the formula were severally treated with phenyl biguanide and ortho tolyl biguanide similarly to the treatment described in Example I and similar protection from gases containing oxides'of nitrogen and sulfur was obtained.
These treatments gave good protection to dye ings on'acetate silk which were dyed with the following compounds:
r m, com I NHCOCH;
' and A large number of biguanides can be used in accordance with the invention and with the effect described in the foregoing examples. Such biguanides, sometimes called blguanidines .o'r guanyl guanidines may be readily prepared by reacting a primary or secondary amine with dicyan diamide in the manner described in Jour. fi;:. prakt. Chem., 84, 396, thereby producing biguanides of the general formula 1 m H wherein R is hydrogen or the substituted group of the secondary amine. Mono-, bisor -trisbiguanides are produced when one, two or three groups are present in the nucleus. Accordingly aniline produces all of which have the described effect of the biguanides mentioned in the foregoing examples. As illustrative of the class of biguanides which are useful for the purposes of the present invention and which may be produced in like manner from arylamines and heterocyclic amines, the following amines are mentioned as the starting materials from which such representative biguanides are made; aniline, o, m and p-toluidines, xylidines, cresidine, 2,5-dimethoxy aniline, monoand di-chlor anilines, o, m and p-cyano aniline, m-amino benz'otrifluoride, 0, m and pamino phenyl methyl sulfone, o, m and p amino acetophenone, p-amino phenyl .beta-hydroxy ethyl ether, 0, m and p-anisidine and phenetidine, p-dodeoyl aniline, p-amino ethyl benzoate, sulfanilamide, p-amino acetanilide, o, m and pphenylene diamine, m-toluene diamine, 2,4-diamino anisol, 2,4-diamino chlorbenzene, benzidine, toluidine dianisidine, 2,4,4'-triamino diphenyl, 1,3,5-triamino benzene, 2,4,6-triamino toluene, 4,4-diamino diphenyl ether, thioaniline, 4,4-diamino diphenyl sulfone, 4,4'-diamino diphenyl urea, p-amino benzoyl m-phenylene diamine, m-amino benzoyl p-phenylene diamine, m-amino benzene sulfonyl m-phenylene diamine, 4,4'-diamino stilbene,1,2-di(4,4-amino-phenoxy) ethane, l,2-di(3-amino phenyl) ethane, 4,4- diamino diphenyl amine, 4,4'-diamino diphenyl methane, 4,4'-di(mono ethyl amino) diphenyl methane, m-amino phenyl methyl pyrazolone, 2- aminol-methyl thiazol, 2-amino benzothiazol, amino tetrazol, 2- and 3-amino pyridine, 2,6- dia-mino pyridine, 2,4,6-triamino pyridine, alpha and beta-naphthylamine, 2-methoxy-l-naphthylamine, 4-amino N-methyl naphtho styril, amino antipyrene, N -methyl aniline, N-ethyl aniline, N- hydroxy ethyl aniline, N-butyl aniline, N-methyl o-toluidine, n-methyl aniline, hydroxy propyl aniline, hydroxy amyl aniline, 2-hydroxy-3 chlor-propyl aniline, 4-amino-diphenyl sulfone and 4-amino diphenyl.
Accordingly, the compounds useful as inhibitors are the mono-, bisand trisbiguanides which may be represented by the formula in which the nuclear radical R is from the benzene, naphthalene or heterocyclic series and the series of diphenyl compounds represented by the formula in which X is one of a group consisting of --O-, -S-, NH, CH2SO2-, CO, -CH:CH2, -CH=CH, NHCO-, N'HCONH, OCH2CHzO--, and NHSO:; and p is an integer not greater than 2. In cases where p is 1, the radical has no bridging group. Any of these nuclei may be unsubstituted or substituted once to twice by any combination of alkyl groups having 1 to 12 carbons, methoxy, ethoxy, CFa, halogen, COCH3, CN, acetylamino, -SO2CH3 and SO2 phenyl. The diphenyl compounds can be substituted in each benzene ring. In the above formula m is 1 to 3 and R is one of a group consisting of hydrogen, alkyl having 1 to 5 carbons and hydroxyalkyl havingl to 5 carbons. The biguanides of the benzene series arethe preferred embodiments, such as those represented by the formula wherein A represents the nuclear substituents heretofore recited and n is 1 or 2, and of these the mono-biguanides are preferred.
The biguanides used in carrying out the invention have good afiinity for cellulose acetate fibers resulting in rapid absorption and good retention by the fiber, but the precise reasons for their inhibiting action are not fully understood. It has been suggested that the inhibiting effect may be due to the formation of salts or oxides by the action of the deleterious fumes on the biguanides in preference to a salt forming or oxidizing action on the dye. The nature of the reaction products is not fully known and it is to be understood that the invention is not limited by the proposed theory.
The invention is especially useful in improving the properties of dyed cellulose acetate fibers which are dyed with the anthraquinone and the monazo dyes, such as 1,4 di[mono hydroxy ethyl amino] anthraquinone, l-methyl amino-a-hydroxy ethyl amino anthraquinone, l-amino-4- methyl amino anthraquinone, 1,4-diamino-5- nitro anthraquinone, l-amino-4-anilidoanthra quinone and 4-amino-4-nitro-azobenzene with which a similar degree of protection is afforded by the biguanides described.
It is commonly preferable to apply the biguanides as an after treatment to the dyed fiber but it may be applied during the dyeing operation by adding the inhibiting compound to the dyebath or other treating bath. Any manner of aifixing or adsorbing the inhibitor on and in the fiber gives beneficial results. A short immersion of the fibers, such as about thirty secends is frequently sufficient to give adequate protection but better results are sometimes obtained with longer immersions, such as three to five minutes. The adsorption of the inhibitor varies somewhat with the various circumstances but it is generally quite rapid. Considerably longer immersions than those mentioned can be employed when they are desired since they are not harmful, but such excessively long immersions are commonly unnecessary. The best duration of time for immersing the fibers may vary somewhat depending on circumstances, such as the particular inhibitor used, the character and condition of the fiber acter of the treating'bath. The wide variation permissible in the treatment is adanta eous since it lends itself desirably to the special circumstances encountered in practice. The fastness of the dyeings is not adversely affected and in most cases it is improved.
From the foregoing disclosure it will be recognized that the inventionis susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations herein set forth.
We claim:
1. A dyed article of cellulose acetate fibers which has affixed to said fibers a biguanide of a group represented by the formula in which R is a nucleus of the benzene, naphthalene heterocyclic and (an (A) series, m is 1 to 3; R is one of a group consisting of hydrogen, alkyl having 1 to 5 carbons and hydroxyalkyl having 1 to 5 carbons; A is from the group consisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy, CFa, halogen, COCHa, CN, acetylamino, SOzCHa and SO: phenyl; n is an integer not greater than 2; X is one of a group consisting of -O-, -S-, NH, CH2SO2, CO-, CH2CH2-, -CH=CH, NHCO--, NHCONH-, OCHaCHaO- and NHSO2-; and p is an'integer not greater than 2.
2. A dyed article of cellulose acetate fibers which has affixed to said fibers phenyl biguanide.
3. A dyed article of cellulose acetate fibers which has aifixed to said fibers phenyl ethyl biguanide.
4. In the process of inhibiting the action of gases which are deleterious to dyeings on cellulose acetate fibers, the steps which comprise wetting the dyed fibers with an aqueous fluid containing a biguanide and then'removing the water so as to affix the biguanide to the fibers, said biguanide being represented by the formula and,the temperature and char-.
in which R is a nucleus of the benzene, naphthalene, heterocyclic and do. n
series, m is i to 3; R is one of a group consisting of hydrogen, alkyl having 1 to 5 carbons, hydroxyalkyl having 1 .to 5 carbons; A is from the group consisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy, CFc, halogen, COOCI-Is, CN, acetylamino, SOzCHa and -SO2 phenyl; n is an integer not greater than 2; X is one of a group consisting of -O-, S-, NH-, CH2SO2-, CO-, CH2CH2-, CH=CH-, -NHCO-, NHCONH-, --OCH2CH2O, and NHSO2-; and p is an integer not greater than 2.
5. In the process of inhibiting the action of gases which are deleterious to dyeings on cellulose acetate fibers, the steps which comprise saturating the dyed fibers with an aqueous fluid containing a biguanide and then removing the water so as to affix the biguanide to the fibers, said biguanide being represented by the formula in which R is a nucleus of the benzene, naphthalene, heterocyclic and series, m is 1 to 3; R is one of a group consisting of hydrogen, alkyl 'having 1 to 5 carbons, hydroxyalkyl having 1 to 5 carbons; A is from the group consisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy, CFz, halogen, COOCHa, CN, acetylamino, SOzCHs and -SO2 phenyl; n is an integer not greater than 2; X is one of a group consisting of -O-, -S, NH--, --CH1SOz-, C0, CH2CH2-, NHCO-, NHCONH-, -OCH2CH20- and NHSO2; and p is an integer not greater than 2.
6. In the process of inhibiting the action of gases which are deleterious to dyeings on cellulose acetate fibers, the steps which comprise wetting the fibers with an aqueous fiuid containing phenyl biguanide and-then removing the water, thereby to affix said biguanide to the fibers.
- '7. In the process of inhibiting the action of gases which are deleterious to dyeings on cellulose acetate fibers, the steps which comprise wet ting the fibers with an aqueous fluid containing phenyl ethyl biguanide.
' JOHN M. TIN'KER.
DONOVAN E. KVALNES.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US318706A US2255090A (en) | 1940-02-13 | 1940-02-13 | Inhibiting the gas fading of dyed acetate silk |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US318706A US2255090A (en) | 1940-02-13 | 1940-02-13 | Inhibiting the gas fading of dyed acetate silk |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2255090A true US2255090A (en) | 1941-09-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US318706A Expired - Lifetime US2255090A (en) | 1940-02-13 | 1940-02-13 | Inhibiting the gas fading of dyed acetate silk |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2433489A (en) * | 1944-01-27 | 1947-12-30 | Boots Pure Drug Co Ltd | Production of amidines |
| US2446421A (en) * | 1944-11-03 | 1948-08-03 | Ici Ltd | Manufacture of arylbiguanide hydrochlorides |
| US2525898A (en) * | 1947-10-09 | 1950-10-17 | Gen Aniline & Film Corp | 1, 3-diphenylimidazolidine and certain derivatives thereof used as acid fading inhibitors |
| US2529935A (en) * | 1947-10-15 | 1950-11-14 | Gen Aniline & Film Corp | Acid-fading inhibition using certain 1, 4-diaryl piperazines |
| US2536640A (en) * | 1948-12-29 | 1951-01-02 | Gen Aniline & Film Corp | Acid-fading inhibition with certain p,p'-diaminodiphenyl-cyclohexane compounds |
| US2684924A (en) * | 1951-02-05 | 1954-07-27 | Ici Ltd | Nu-chlorophenyldiguanidino compounds |
| US2690455A (en) * | 1952-07-24 | 1954-09-28 | American Cyanamid Co | Ethylene bis-arylbiguanides and process of preparing same |
| DE937886C (en) * | 1952-09-18 | 1956-01-19 | Basf Ag | Process for finishing dyed blended fabrics made from cellulose acetate fibers and from fibers based on native or regenerated cellulose |
| DE954325C (en) * | 1952-09-18 | 1956-12-13 | Basf Ag | Process for finishing dyed blended fabrics |
| US3118937A (en) * | 1959-06-16 | 1964-01-21 | Ciba Geigy Corp | 4, 4'-bis-biguanidostilbenedisulfonamides |
| US3136816A (en) * | 1960-03-14 | 1964-06-09 | Sterling Drug Inc | 1-(lower alkylmercapto-chloro-phenyl) biguanides |
| US3468898A (en) * | 1966-05-26 | 1969-09-23 | Sterling Drug Inc | Bridged bis-biguanides and bis-guanidines |
| US3769013A (en) * | 1968-08-07 | 1973-10-30 | Mita Industrial Co Ltd | Wet type diazotype developer |
| US20080026025A1 (en) * | 2006-07-26 | 2008-01-31 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
| US20090191250A1 (en) * | 2008-01-28 | 2009-07-30 | Water Visions International, Inc. | Antimicrobial Composite Material and Method for Fluid Treatment |
-
1940
- 1940-02-13 US US318706A patent/US2255090A/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2433489A (en) * | 1944-01-27 | 1947-12-30 | Boots Pure Drug Co Ltd | Production of amidines |
| US2446421A (en) * | 1944-11-03 | 1948-08-03 | Ici Ltd | Manufacture of arylbiguanide hydrochlorides |
| US2525898A (en) * | 1947-10-09 | 1950-10-17 | Gen Aniline & Film Corp | 1, 3-diphenylimidazolidine and certain derivatives thereof used as acid fading inhibitors |
| US2529935A (en) * | 1947-10-15 | 1950-11-14 | Gen Aniline & Film Corp | Acid-fading inhibition using certain 1, 4-diaryl piperazines |
| US2536640A (en) * | 1948-12-29 | 1951-01-02 | Gen Aniline & Film Corp | Acid-fading inhibition with certain p,p'-diaminodiphenyl-cyclohexane compounds |
| US2684924A (en) * | 1951-02-05 | 1954-07-27 | Ici Ltd | Nu-chlorophenyldiguanidino compounds |
| US2690455A (en) * | 1952-07-24 | 1954-09-28 | American Cyanamid Co | Ethylene bis-arylbiguanides and process of preparing same |
| DE937886C (en) * | 1952-09-18 | 1956-01-19 | Basf Ag | Process for finishing dyed blended fabrics made from cellulose acetate fibers and from fibers based on native or regenerated cellulose |
| DE954325C (en) * | 1952-09-18 | 1956-12-13 | Basf Ag | Process for finishing dyed blended fabrics |
| US3118937A (en) * | 1959-06-16 | 1964-01-21 | Ciba Geigy Corp | 4, 4'-bis-biguanidostilbenedisulfonamides |
| US3136816A (en) * | 1960-03-14 | 1964-06-09 | Sterling Drug Inc | 1-(lower alkylmercapto-chloro-phenyl) biguanides |
| US3468898A (en) * | 1966-05-26 | 1969-09-23 | Sterling Drug Inc | Bridged bis-biguanides and bis-guanidines |
| US3769013A (en) * | 1968-08-07 | 1973-10-30 | Mita Industrial Co Ltd | Wet type diazotype developer |
| US20080026025A1 (en) * | 2006-07-26 | 2008-01-31 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
| US7427409B2 (en) | 2006-07-26 | 2008-09-23 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
| US20080272062A1 (en) * | 2006-07-26 | 2008-11-06 | Water Visions International, Inc. | Broad spectrum antimicrobial purification devices and methods for purifying fluids |
| US20080306301A1 (en) * | 2006-07-26 | 2008-12-11 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
| US20090191250A1 (en) * | 2008-01-28 | 2009-07-30 | Water Visions International, Inc. | Antimicrobial Composite Material and Method for Fluid Treatment |
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