US2668777A - Whitening agents for organic materials - Google Patents

Whitening agents for organic materials Download PDF

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Publication number
US2668777A
US2668777A US119757A US11975749A US2668777A US 2668777 A US2668777 A US 2668777A US 119757 A US119757 A US 119757A US 11975749 A US11975749 A US 11975749A US 2668777 A US2668777 A US 2668777A
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compounds
organic materials
whitening
disulfonic acid
whitening agents
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US119757A
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Gold Heinrich
Petersen Siegfried
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/22—Naphthotriazoles
    • C07D249/24—Naphthotriazoles with stilbene radicals directly attached in position 2

Definitions

  • the present invention relates to new whitening agents for organic materials, and to a treatment processing of fibrous materials such as paper and textile materials, is usually called whitening or optical bleaching.
  • whitening or optical bleaching a treatment processing of fibrous materials such as paper and textile materials.
  • a number of chemically widely different compounds has already been proposed, compounds which show differences partly in their optical behavior, partly in other properties.
  • an exceptional whitening effect on organic materials is achieved by means of salts of sulfonic acids of such substantive compounds as contain several 1,2,3- triazole rings per molecule.
  • These compounds are derived from diamines such as benzidine or diaminostilbene disulfonic acid.
  • diamines such as benzidine or diaminostilbene disulfonic acid.
  • 4,4- bis [5' sulfonaphtho 1,2':4,5 triazolyl (2) l-stilbene-2,2-disulfonic acid are distinguished by an exceptional strength.
  • the compounds in question may be obtained in the usual manner by tetrazotizing the said amines, coupling the tetrazo compounds with amines which couple in a position adjacent to the amino group-for instance with 2-amino naphthalene or its sulfonic acids or their substitution products-and converting the ortho-amino azo compounds thus obtained in known manner into the triazoles.
  • the compounds according to the invention show weak greenish to violet fluorescence, and Their application takes place in the usual manner.
  • textile materials of cotton or regenerated cellulose the compounds on account of their sub- 'stantive properties can simply by applied from a rinsing bath to the 'fibrousmaterial. Usually In the treatment their application to textile materials will be effected. in the laundering or finishing process.
  • the whitening compounds For such applications it is possible simply to add the whitening compounds to detergents to be sold, such as soap, soap substitutes, washing powders, and to finishing agents such as starch.
  • the compounds may either be already admixed to thedyestufi, or added to the dye bath, or finally mixed up with the discharge paste.
  • the treatment with these compounds has also a favorable effect on dyed textile materials, since in many cases thus a clearer and more vivid shade is obtained.
  • Our new agents can also be used for whitening wool; in this case a treatment in an acid bath at elevated temperature, say to (1., is expedient.
  • thecompounds are used in the form of their alkali, ammonium or alkaline earth salts; in case a soldbility of the salts in organic solvents is required, it is expedient to use the salts of amines.
  • the compounds according to the invention show the advantage of highest substantivity. in addition to excellent fastness to washing, to boiling soda and to chlorine, and good fastness to light;
  • the members The present invention is illustrated by the fol-: lowing examples; it is, however, not restricted thereto:
  • Example 1 The fabric to be whitened is -treated for minutes at a temperature of 40 C. with a liquor containing 0.05 to 0.06 gram of l,5l'-bis-[5'-sulfonaphtho 1',2:4,5 triazolyl (2)] stilbene 2,2-disulfonic acid per liter, rinsed and dried.
  • the material thus obtained shows a better whitetint than without this aftertreatment.
  • the compound applied is obtained by tetra,- zotizing 4,4-diaminostilbene-2,2f-disulfonic acid, coupling with 2 mols of 2-aminonaphthalene-5- sul'fonic acid and boiling the dyestuff obtained with ammoniacal copper sulfate solution.
  • the same compound can be obtained by oxidizing the disazo-dyestuif from tetrazotized 4,4'-diaminostilbene-2,2'-disulfonic acid and 2 mols of 1- ami'nonaphthalene-5-sulfonic acid with ammoniacal copper sulfate.
  • Example 2 Yellowish white paper is treated with a solution containing 0.05 to 0.06 gram per liter of the compound mentioned in example one. After rinsing and drying the paper shows a distinct whitening effect.
  • Example 3 A slightly yellowish nettle cloth is treated at atemperature of 40 C. in a rinsing bath containing 0.018 gram of 4,4-bis-[5'sulfonaphtho- -1',2':.4,5 triazolyl (2)] stilbene 2,2disulfonic acid and 0.038 gram of [,stilbene-(Ml) lbis-[w-phenylurealelz-disulfonic acid, which urea can be obtained from 1 mol of 4,4' -diaminostilbene-2,2-disulfonic acid and 2 mols of phenylisocyanate. After rinsing and drying, the material shows a perfectly white, neutral, optical bleaching effect which remains unchanged also, after washing at the boil and the usual household bleaching.
  • Example 4 For a normal washing of white goods a washing agent is used which contains, besides the usual washing and cleansing agents and other admixtures, 2 to 3, grams of a. mixture of 4,47- bis [5. sulfonaphtho l',2':4,5 triazolyl- (2)[lstilb,ene-2,2'-disulfonic acid (18 parts) and Estilbene (4,4)] bis [w phenylureal 2,2- disulfonic acid (38 parts) per kilogram. After rinsing and drying the material shows a neutral optical bleaching eifect.
  • Example 5 Cotton is dyed in the usual way with 4 per cent of the dyestufi No. 670, Farbstofitabellen by Gustav Schultz, 7th edition. The dyeing thus obtained is discharged with a neutral Rongalite discharge paste, which contains 0.1 to 0.2 per cent of thecompound mentioned in. example one. cent of the compound mentioned in Example 1. The discharge appears whiter than without the addition of the whitening agent.
  • a similar white discharge eifect is obtained if in dyeing with the same dyestuif 0.05 to 0.01 per cent of the compound mentioned in Example 1 isadded to. the, dye. bath, and thereafter a neu- 1 tral Rongalite discharge is carried through.
  • Example 6 W001 is boiledfor 20 minutes in a bath containing 0.05. gram of MU-bis-[5'-sulfonaphtho- 1,2.':,4,5 triazolyl (2)] stilbene 2,2 disulfonic acid and 0.75 gram of sulfuric acid of 96 B. per liter. The material thus obtained shows a purer white than without this aftertreatment. A good eifect can already be obtained at a temperature of 40 to 50 C.
  • X stands for a vinylene and m for a whole number from 0' to 1, and salts of such acids selected from the group consisting of the alkali metal, ammonium, alkaline earth and amine salts, said compounds being substantially colorless and possessing an excellent whitening efiect.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Ing
are highly substantive.
Patented Feb. 9, 1954 WHITENING AGENTSFOR ORGANIC MATERIALS Heinrich Gold, Opladen, and Siegfried Petersen, Leverkusen- Schlebusch, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Application October 5, 1949, Serial No. 119,757
Claims priority, application Switzerland October 16, 1948 8 Claims. (Cl. 117-335) The present invention relates to new whitening agents for organic materials, and to a treatment processing of fibrous materials such as paper and textile materials, is usually called whitening or optical bleaching. For this purpose a number of chemically widely different compounds has already been proposed, compounds which show differences partly in their optical behavior, partly in other properties.
According to this invention, an exceptional whitening effect on organic materials is achieved by means of salts of sulfonic acids of such substantive compounds as contain several 1,2,3- triazole rings per molecule. These compounds are derived from diamines such as benzidine or diaminostilbene disulfonic acid. As an example of the new compounds may be mentioned 4,4- bis [5' sulfonaphtho 1,2':4,5 triazolyl (2) l-stilbene-2,2-disulfonic acid. The compounds derived from stilbene are distinguished by an exceptional strength. The compounds in question may be obtained in the usual manner by tetrazotizing the said amines, coupling the tetrazo compounds with amines which couple in a position adjacent to the amino group-for instance with 2-amino naphthalene or its sulfonic acids or their substitution products-and converting the ortho-amino azo compounds thus obtained in known manner into the triazoles.
The compounds according to the invention show weak greenish to violet fluorescence, and Their application takes place in the usual manner. of textile materials of cotton or regenerated cellulose, the compounds on account of their sub- 'stantive properties can simply by applied from a rinsing bath to the 'fibrousmaterial. Mostly In the treatment their application to textile materials will be effected. in the laundering or finishing process.
For such applications it is possible simply to add the whitening compounds to detergents to be sold, such as soap, soap substitutes, washing powders, and to finishing agents such as starch. For producing discharge effects of improved whiteness on colored textile materials, the compounds may either be already admixed to thedyestufi, or added to the dye bath, or finally mixed up with the discharge paste. It may be mentioned that the treatment with these compounds has also a favorable effect on dyed textile materials, since in many cases thus a clearer and more vivid shade is obtained. Our new agents can also be used for whitening wool; in this case a treatment in an acid bath at elevated temperature, say to (1., is expedient. In the paper industry the application takes place either in a dipping process in the case of finished papers, or by adding the compounds to the paper pulp during the manufacture. This application is not only of interest for ordinary papers, but also for special papers such as photographic papers. Since the compounds causing the whitening effect possess the property of absorbing ultraviolet light, paper or other wrapping materials treated therewith are suited for protecting materials sensitive to light, such as victuals and the like. Also with other organic materials to be bleached, such as plastics, artificial silk, light leathers, straw for hats, wood, soap and so on, the effective compounds are incorporated either in the final state or in any phase of their manufacture, just as it proves expedient or desirable. In all cases the whitish materials are considerably improved in their white appearance by this treatment. The whitening effect achieved with said compounds can considerably be increased in many cases by adding, if other conditions permit, salts e. g. Glaubers salt to the bath.
According to the field of application thecompounds are used in the form of their alkali, ammonium or alkaline earth salts; in case a soldbility of the salts in organic solvents is required, it is expedient to use the salts of amines.
Compared with the compounds already used or proposed for the optical bleaching, the compounds according to the invention show the advantage of highest substantivity. in addition to excellent fastness to washing, to boiling soda and to chlorine, and good fastness to light; The members The present invention is illustrated by the fol-: lowing examples; it is, however, not restricted thereto:
Example 1 The fabric to be whitened is -treated for minutes at a temperature of 40 C. with a liquor containing 0.05 to 0.06 gram of l,5l'-bis-[5'-sulfonaphtho 1',2:4,5 triazolyl (2)] stilbene 2,2-disulfonic acid per liter, rinsed and dried.
The material thus obtained shows a better whitetint than without this aftertreatment.
The compound applied is obtained by tetra,- zotizing 4,4-diaminostilbene-2,2f-disulfonic acid, coupling with 2 mols of 2-aminonaphthalene-5- sul'fonic acid and boiling the dyestuff obtained with ammoniacal copper sulfate solution. The same compound can be obtained by oxidizing the disazo-dyestuif from tetrazotized 4,4'-diaminostilbene-2,2'-disulfonic acid and 2 mols of 1- ami'nonaphthalene-5-sulfonic acid with ammoniacal copper sulfate. If instead of l-aminonaphthal'eneor 2-aminonaphthalene-5-sulfonic acid, 2 amino 5 methoxynapththalene '7- sulfonic acid or 2-amino-8-methoxy-naththalene-fi-sulfonic acid is used as coupling component, compounds are obtained the fluorescence of which appears less greenish.
Example 2 Yellowish white paper is treated with a solution containing 0.05 to 0.06 gram per liter of the compound mentioned in example one. After rinsing and drying the paper shows a distinct whitening effect.
The same effect can be achieved by the addition of 0.1 to 1 per cent of the same compound to the usual paper pulp.
Example 3 A slightly yellowish nettle cloth is treated at atemperature of 40 C. in a rinsing bath containing 0.018 gram of 4,4-bis-[5'sulfonaphtho- -1',2':.4,5 triazolyl (2)] stilbene 2,2disulfonic acid and 0.038 gram of [,stilbene-(Ml) lbis-[w-phenylurealelz-disulfonic acid, which urea can be obtained from 1 mol of 4,4' -diaminostilbene-2,2-disulfonic acid and 2 mols of phenylisocyanate. After rinsing and drying, the material shows a perfectly white, neutral, optical bleaching effect which remains unchanged also, after washing at the boil and the usual household bleaching.
Example 4 For a normal washing of white goods a washing agent is used which contains, besides the usual washing and cleansing agents and other admixtures, 2 to 3, grams of a. mixture of 4,47- bis [5. sulfonaphtho l',2':4,5 triazolyl- (2)[lstilb,ene-2,2'-disulfonic acid (18 parts) and Estilbene (4,4)] bis [w phenylureal 2,2- disulfonic acid (38 parts) per kilogram. After rinsing and drying the material shows a neutral optical bleaching eifect.
Example 5 Cotton is dyed in the usual way with 4 per cent of the dyestufi No. 670, Farbstofitabellen by Gustav Schultz, 7th edition. The dyeing thus obtained is discharged with a neutral Rongalite discharge paste, which contains 0.1 to 0.2 per cent of thecompound mentioned in. example one. cent of the compound mentioned in Example 1. The discharge appears whiter than without the addition of the whitening agent.
A similar white discharge eifect is obtained if in dyeing with the same dyestuif 0.05 to 0.01 per cent of the compound mentioned in Example 1 isadded to. the, dye. bath, and thereafter a neu- 1 tral Rongalite discharge is carried through.
Example 6 W001 is boiledfor 20 minutes in a bath containing 0.05. gram of MU-bis-[5'-sulfonaphtho- 1,2.':,4,5 triazolyl (2)] stilbene 2,2 disulfonic acid and 0.75 gram of sulfuric acid of 96 B. per liter. The material thus obtained shows a purer white than without this aftertreatment. A good eifect can already be obtained at a temperature of 40 to 50 C.
We claim:
1. A compound of the group consisting ofjacids of the general formula:
wherein X stands for a vinylene and m for a whole number from 0' to 1, and salts of such acids selected from the group consisting of the alkali metal, ammonium, alkaline earth and amine salts, said compounds being substantially colorless and possessing an excellent whitening efiect.
2. A compound of the general formula:
5 6. 4,4 bis [5' sulfonaphtho 1,2':4,5- triazo1y1-(2) ]-sti1bene-2,2'-disulfonic acid.
7. Sodium salts of 4,4-bis-[5'-sulfonaphtho 1',2' :4,5-triazo1y1- (2) -sti1bene-disulfonic acids.
8. The sodium salt of 4,4'-bis-[5-su1fonaph- 5 the 1',2':4,5 triazolyl (2)] sti1bene2,2-disulfonic acid.
HEINRICH GOLD. SIEGFRIED PETERSEN.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,462,405 Keller Feb. 22, 1949 2,467,262 Knight Apr. 12, 1949 OTHER REFERENCES Ser. No. 381,856, Wendi; (A. P. 0.), published May 11, 1943.

Claims (2)

1. A COMPOUND OF THE GROUP CONSISTING OF ACIDS OF THE GENERAL FORMULA:
3. WHITE ORGANIC MATERIALS HAVING INCORPORATED THEREIN AN EFFECTIVE AMOUNT OF A WHITENING AGENT AS DEFINE IN CLAIM 1.
US119757A 1948-10-16 1949-10-05 Whitening agents for organic materials Expired - Lifetime US2668777A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733165A (en) * 1956-01-31 Naoas
DE955418C (en) * 1954-03-19 1957-01-03 Geigy Ag J R Process for the preparation of fluorescent stilbylditriazole compounds
DE1001273B (en) * 1954-03-31 1957-01-24 Geigy Ag J R Process for the preparation of optical brightening agents
US2784183A (en) * 1951-09-06 1957-03-05 Geigy Ag J R Fluorescent monotriazole compounds
US2784184A (en) * 1957-03-05 - methyl -
US2784197A (en) * 1957-03-05 Fluorescent stilbyl ditriazole
DE1018066B (en) * 1954-03-19 1957-10-24 Geigy Ag J R Process for the preparation of fluorescent stilbylditriazole compounds
US2838504A (en) * 1955-04-21 1958-06-10 Sterling Drug Inc Benzimidazolylstilbene whitening and brightening agents
US2845419A (en) * 1955-02-15 1958-07-29 Ciba Ltd Oxadiazole compounds
US2924549A (en) * 1955-12-15 1960-02-09 Bayer Ag Paper containing an organic fluorescent dye
US2927866A (en) * 1954-11-12 1960-03-08 Gen Aniline & Film Corp Bis p, p(p.methoxy, meta-methyl benzotriazolyl) stilbene o, o'-disulfonic acid disodium salt
US3075853A (en) * 1960-08-08 1963-01-29 Norton Co Pressure sensitive adhesive tape
US3145104A (en) * 1959-08-07 1964-08-18 Gisela K Oster Photographic processes comprising cross-linking of thiol polymers
US3205202A (en) * 1955-08-10 1965-09-07 Bayer Ag Process for improving the brightness of synthetic polymers and products resulting therefrom
US3416923A (en) * 1964-08-24 1968-12-17 Eastman Kodak Co Amide dispersant for fluorescent agents in photographic elements

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH229350A (en) * 1941-11-05 1943-10-15 Ag J R Geigy Process for the preparation of a direct drawing copper-containing dye.
GB596405A (en) * 1945-04-12 1948-01-02 Unilever Ltd Improvements in the washing of textiles and in detergents therefor
US2462405A (en) * 1944-11-24 1949-02-22 Geigy Ag J R Stilbene bis triazole azo dyestuffs
US2467262A (en) * 1945-04-11 1949-04-12 Ici Ltd Stilbene triazole azo dyes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH229350A (en) * 1941-11-05 1943-10-15 Ag J R Geigy Process for the preparation of a direct drawing copper-containing dye.
US2462405A (en) * 1944-11-24 1949-02-22 Geigy Ag J R Stilbene bis triazole azo dyestuffs
US2467262A (en) * 1945-04-11 1949-04-12 Ici Ltd Stilbene triazole azo dyes
GB596405A (en) * 1945-04-12 1948-01-02 Unilever Ltd Improvements in the washing of textiles and in detergents therefor

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784184A (en) * 1957-03-05 - methyl -
US2784197A (en) * 1957-03-05 Fluorescent stilbyl ditriazole
US2733165A (en) * 1956-01-31 Naoas
US2784183A (en) * 1951-09-06 1957-03-05 Geigy Ag J R Fluorescent monotriazole compounds
DE955418C (en) * 1954-03-19 1957-01-03 Geigy Ag J R Process for the preparation of fluorescent stilbylditriazole compounds
DE1018066B (en) * 1954-03-19 1957-10-24 Geigy Ag J R Process for the preparation of fluorescent stilbylditriazole compounds
DE1001273B (en) * 1954-03-31 1957-01-24 Geigy Ag J R Process for the preparation of optical brightening agents
DE1001273C2 (en) * 1954-03-31 1957-07-04 Geigy Ag J R Process for the preparation of optical brightening agents
US2927866A (en) * 1954-11-12 1960-03-08 Gen Aniline & Film Corp Bis p, p(p.methoxy, meta-methyl benzotriazolyl) stilbene o, o'-disulfonic acid disodium salt
US2845419A (en) * 1955-02-15 1958-07-29 Ciba Ltd Oxadiazole compounds
US2838504A (en) * 1955-04-21 1958-06-10 Sterling Drug Inc Benzimidazolylstilbene whitening and brightening agents
US2937148A (en) * 1955-04-21 1960-05-17 Sterling Drug Inc Detergent compositions comprising benzimidazolylstilbene whitening and brightening agents
US3205202A (en) * 1955-08-10 1965-09-07 Bayer Ag Process for improving the brightness of synthetic polymers and products resulting therefrom
US2924549A (en) * 1955-12-15 1960-02-09 Bayer Ag Paper containing an organic fluorescent dye
US3145104A (en) * 1959-08-07 1964-08-18 Gisela K Oster Photographic processes comprising cross-linking of thiol polymers
US3075853A (en) * 1960-08-08 1963-01-29 Norton Co Pressure sensitive adhesive tape
US3416923A (en) * 1964-08-24 1968-12-17 Eastman Kodak Co Amide dispersant for fluorescent agents in photographic elements

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