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Publication numberUS3423407 A
Publication typeGrant
Publication dateJan 21, 1969
Filing dateOct 30, 1967
Priority dateOct 30, 1967
Publication numberUS 3423407 A, US 3423407A, US-A-3423407, US3423407 A, US3423407A
InventorsSigmund C Catino, Albert F Strobel
Original AssigneeGaf Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
4,4'-bis(4,6-di(chloroanilino)-s-triazin-2-ylamino) - 2,2' - stilbenedisulfonic acid brighteners
US 3423407 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

nt; choose 23/00 Patented Jan. 21, 1969 Ue wd S ew Pwm Ofice I 3,423,407 4,4-BIS[4,6-DI(CHLR0ANILIN0)-S-TRIAZIN-2- YLAMINO] 2,2 STILBENEDISULFONIC ACID BRIGHTENERS Albert FIStrobel, Delmar, and Sigmund C. Catino, Castleton, N.Y.,-assignors to GAF Corporation, New York, N.Y., a corporation of Delaware lNo Drawing. Continuation of application Ser. No. 382,364, July 13, 1964. This application Oct. 30, 1967, Ser. No. 679,259

U.S. Cl. 260----240v 2 Claims ABSTRACT or THE'DISCLOSURE' wherein R represents a member of the group consisting The use of fluorescent brightening or whitening agents (hereinafter referred to as brightening agents) to brighten and whiten textiles, paper and the like is well known in the art. The usual fluorescent brightening agent is a substantially colorless compound which however has a bluish fluorescence under ultraviolet light so that the bluish fluorescence of the agentwill neutralize any yellowness of the fibrous material with which it is used and make it appear Whiter or brighter.

One of the largest uses of such brightening agents is in laundering of textiles. However, many of the known fluorescent brightening agents are sensitive to hypochlorite bleach which is frequently used in both home and commercial laundries. Also many brightening agents which are effective on cotton or other cellulosic fibers, have little or no effect on wool or synthetic fibers, and thus are relatively ineflective on mixed textiles, and when incorporated in a detergent are effective only on cotton,

of hydrogen and chlorine. These fluorescent brightening etc. but ineffective on synthetics.

agents which are characterized by a 4-anilino or 3,4- anilino substituent in each of the 4- and 6-positions of the triazine rings are characterized by a high degree of stability tojhypochlorite bleach, which is frequently used in laundering.

This application is a continuation of our copending application Ser. No. 382,364 filed July 13, 1964, now


This invention relates to a new and improved process 60 and composition for brightening and whitening fibrous materials.

It is therefore an object of this invention to provide a process and composition for whitening both cotton and synthetic goods.

We have discovered that certain 4,4'-bis[4,6-(chloro- 40 anilino)-2-triazin-2-ylamino]-2,2'-stilbenedisulfonic acids of the formula:

wherein w, x, y and z are 1 or 2, and M is a cation, e.g., H, alkali metal (Na, K, Li, etc.) alkaline earth metal (Ca, Si, Mg, etc.), NH or hydroxyalkyl amino etc.) dye cotton and nylon when applied from an aqueous T h e pH was kept slightly alkaline to phenolphthaleln detergent or soap bath or a separate bath. They are with 100 cc. of 20% soda ash. It was steam distilled to characterized by a high degree of stability to hypochloremove pf l' cgoledafiltemd and Wah6d Wilh rite bleach which is frequently used in laundries. Water, then dried an 80 y We1ght=435 To prepare these compounds one mol of 4,4'-diamino- 5 x= Application of this brightener to cotton was carried out as follows using a sodium stearate soap Wash bath:

A mixture was prepared of 25 cc. of 1.6% soap solution (8% soap on the weight of the fabric), 125 cc. of

2,2-stilbenedisulfonic acid is reacted with 2 mols of cyanuric chloride in known manner. One mol of this product is then reacted in known manner with 4 mols of mono or dlchloro'amhrie or p'chloroimlhne 10 water and an aliquot of a brightener solution (0.08% i P 26'd1ch1Om or brightener o.w.s.) prepared by dissolving the brightening dlchloro-amllne, elther stepwise, 1.e., one, two, three or agent with a Kmaxz37'5 in of dimethy1form four mols at a time, wherein the chloroaniline derivative amide f ll d by dilution to a 1 liter with Water Aft used in the different steps is the same or difierent chlorowarming to 13 1 of a solution of sodium hypo. aniline derivative, H1015 Of a single chloroaniline 15 chlorite containing 2 g. of available chlorine' 'per liter derivative or mixture of chloroaniline derivatives can be wa added. After 'standing15 min. a 5 g} piece of Cotton condensed in one step. This latter procedure is preferably fabric was added. The washing mixture was agitated at employed, however, when the chloroaniline substituent 130 F. for min., the fabric removed, rinsed. and air is to be the same in all positions and only a single chlorodried at 40 C. aniline derivative is used, as otherwise a mixture of prod- 20 In a similar. fashion an equimolecular amount of the not is obtained. brightener free from halogen atoms: 1

\ SOaNa SOsNa The following examples illustrate the invention:

was applied to cotton from a soap-hypochlorite bath.

The brightness obtained on the cotton was less than half Preparation and application of 4,4-bis[4,6-di(4-chlorothat obtained from the chloro containing brightener anilino) 2-triazin-2-ylamino]-2,2'stilbenedisulfonic acid bove,

of the formula:

II N SOzNa SOaNCt \C/ At 30 C. was dissolved 15 g. of cyanuric chloride in Example 2 65 cc. of acetone. The solution was added in a thin stream Preparation and application of l [4541i to a stirring mixture of 20 cc. of water and 100 g. of ice hl I chips. Then at 8 C. to +3 C., there was added 113.5 3 221; :32, S tnazm 2 ylammo] smbene cc. of a solution of 4,4-diamino-2,2'-stilbenedisulfonic Example 1 N N 1 :v

\C/ (31 SO Na SOsNa \C/ (ill acid (.04 mol). The pH was kept neutral to congo paper by the addition of 25 cc. of 20% soda ash solution. It was stirred 1 hour at 0 C. to negative amine test. Then there was added 11 g. of p-chloroaniline (.08 mol). The material was stirred and temperature was allowed to rise to 25 C. over a 2 hour eriod kee in H faintl basic to brilliant yellow paper svith 25 cc. of 2 0% sodiiim hypound of Examp 1e thls bnghtener gave Shghtly lower brightness than the tetrachloro brightener of Example l droxide. The mixture was filtered cold and the precipitate was transferred to a 1 liter flask. There was added 75 g. and definitely hgher bnghmess than the bnghtaner:

SOaNa SOaNa ""b of p-chloroaniline and 25 mls of water. The mixture was stirred 1 hour at 60 C., then 24 hours at 95 100 C. applied at equimolecular concentration.

This compound is prepared in the same manner as the compound of Example 1 using an equimolecular 50 amount of m-chloroaniline in place of the p-chloroaniline of Example 1.

On application to cotton in the manner of the com- 5 6 Example 3 tered, washed with water, then dried in. an. 80 C. air *Pfeplration n b 4 w oven to give the brightener of the formulafirst given in this example.

dlchloroamlmo) s tnazm 2 ylammo} m. This brightener was applied to nylon cloth (5 g.) by

benedisulfonic acid:

C] v C1 C1 M150 C NH C -CH="C H-'- NH-C CNH" o1 H C O N O N N\ /N Cl C l S a a S 5 a I This compound is made in the samemanner as' the themethod described in Example l (.omitting the addition compound of Example 1 substituting an eq'uimolecular of sodium hypochlorite) It gives a visible whitening to amount of 3,4-dichloroaniline for the p-chloroanilin'e nylon under these conditions, at least equal to the whitenused in Example 1. ing effect obtained from:

" I W I I s I v 7 If 1 ii N hi .1 'SOSNQ some \C/ Application to cotton in the presence of sodium hypochlorite bleach gave similar brightness to the compound 30 applied by the same method.

-' E l 5 of Example 1. Xamp 6 p e"; Preparation and application with alkyl aryl sulfonate V 7 detergent of 4,4 bis[4,6 di(chloroanilino) s triazin- Preparation and application to nylon of 4,4'-bis[4- 2-ylamino]-2,2'-stilbenedisulfonic acid. (p-chloroanilino) 6 (3,4 dichloroanilino) s -triazin- In place of sodium stearate soap used in Example 1,

2-ylamino]-2,2-stilbenedisulfonic acid: there was used 8% of alkyl aryl sulfonate detergent SOaNa SOaNa At 30 C. was dissolved g. of cyanuric chloride in (Tide) on the weight of the fiber. Again sodium hypo- 65 cc. of acetone. The solution was added in a thin stream chlorite was used as in Example 1. Again the whitening to a stirring mixture of cc. of water and 100 g. of ice effect was distinctly greater on cotton than the whitening chips. Then at -s c. to +3" c., there was added 1 13.5 effect obtained with the nonchlorinated 4,4-bis(4,6-dianicc. of a solution of 4,4'-diamino-2,2-stilbenedisulfonic lino s triazin 2 ylamino) 2,2 stilbenedisulfonic acid (.04 mol). The pH Was kept neutral to congo paper acid. by the addition of 25 cc. of 20% soda ash solution. It Was As indicated by the above examples, the novel brightenstirred 1 hour at 0 C. to a negative amine test. Then there ing agents of this invention are usually used in the form was added 11 g. of p chloroaniline (.08 mol). The mateof their sodium salts, however, other alkali metal salts are rial was stirred and temperature was allowed to rise to equally effective and may be obtained in analogous man- 25 C. over a 2-hour period keeping the pH faintly basic ner by using other alkali metal carbonates or hydroxide to brilliant yellow paper with 25 cc. of 20% sodium hy- (e.g., potassium carbonate and hydroxide) in place of the dr-oxide. The mixture was filtered cold. The compound soda ash and NaOH used in the examples. The free acid obtained at this stage is of the formula: of brightening agent may be obtained by acidification with 1i i I it h SOaNa SO Na \C/ This precipitate was transferred to a 1 liter flask. There strong mineral acids such as HCl and H 50 and other was added g. of 3,4-dichloroaniline and 25 mls. of salts may be produced by neutralization of the free acid water. The mixture was stirred 1 hour at 60 C., then 24 with the appropriate base to form the desired salts. The hours at -100 C. The pH was kept slightly alkaline to alkaline earth metal salts are particularly effective for phenolphthalein with cc. 20% soda ash. It was steam whitening photographic paper, etc. distilled to remove excess 3,4-dichloroaniline, cooled, fil- 75 While for use with textiles the novel fluorescent agents 3,423,407 -7 8 are advantageously compounded with the detergent used We claim: for laundering, it will be understood that they can be 1. The fluorescent brightening agent selected from the group consisting of the free acid and salts of the disulequally well applied in a separate bath or added to a ionic acid.

2. The fluorescent brightening agent selected from the group consisting of the free acid and salts of the disul er, along with softening agents, etc.,

' fonic acid.

bleach or rinse Wat if desired.'

References Cited UNITED STATES PATENTS 3/1954 Hein 260-240

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2671784 *Apr 29, 1952Mar 9, 1954American Cyanamid CompanyChlorine-fast fluorescent optical
US2945762 *Oct 12, 1955Jul 19, 1960Eastman Kodak CoSupersensitization of photographic emulsions using triazines
FR1337061A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5024786 *Oct 27, 1988Jun 18, 1991Sandoz Ltd.Detergent compositions containing an anionic surfactant and a 4,4'-bis(triazinylamino)-stilbene disulphonic acid optical brightener
US5863459 *May 9, 1997Jan 26, 1999Sun Chemical CorporationFluorescent yellow azo pigments
US5904878 *May 14, 1997May 18, 1999Sun Chemical CorporationFluorescent orange azo pigments
U.S. Classification544/193.2, 510/324, 252/301.23
International ClassificationD06L3/12
Cooperative ClassificationD06L3/12
European ClassificationD06L3/12