US2643197A - Fluorescent alkoxy benzoyl derivatives of 4,4' diamino stilbene-2,2' disulfonic acidand detergent compositions containing same - Google Patents

Description

Patented June 23, 1953 FLUORESCENT ALKOXY. BENZOYL DERIVA- TIVES OF 4,4 DIAMINO STlLBENE-2,2 DI- SULFONIC ACID AND DETERGENT COM- POSITIONS CONTAINING SAME 1 Leslie Noel Savldge, Burton, and Richard Thomas,

Bromborough, England, assignors to Lever Brothers Company, Cambridge, Mass, at corporation of Maine No Drawing. Application March 30, 1948, Serial No. 18,066. In Great Britain April 3, 1947 20 Claims. (Cl. 11733.5)

This invention relates to methods of treating materials with blue-fluorescent substances so as to impart to the materials blue-fluorescent effects, with or without detergents. The invention also relates to new blue-fluorescent agents suitable for use with these methods, including detergent containing compositions.

The present invention is particularly concerned with the treatment of materials, such as, for example, textiles or paper, with fluorescent substances which, without substantially altering the colour of the treated material, are capable of imparting to it "a blue fluorescence, that is a fluorescence in which at least a major part of the. absorbed ultra-violet light is re-emitted within the blue portion of the spectrum. Substances of this description are laerein termed bluefluorescent substances.

The characteristic properties of blue-fluorescent substances, namely the absorption of ultraviolet radiations and the re-emission of at least some of the absorbed invisible light as visible light in the form of blue fluorescence, have been made use of for a variety of purposes.

The principal use to which these properties have been put is to the correction or neutralisation of the yellowish or ofi-white tint of materials such as textile articles, fabric or yarn, or of paper, and so to the improvement of the whiteness of such materials, by incorporating therein blue-fluorescent substances, for example by treating the materials with a dilute aqueous solution or one or more of the substances. The blue fluorescence acquired by the treated mate: rials not only increases the amount of the reflection in the blue region of the spectrum so as to balance the reflection in'the yellow region, but the total amount of reflected light is-increased by the conversion of invisible ultra-violet light into visible light. The result is to produce an increased total reflection of visible light causing an increased brightness as well as an improved whiteness.

In a similar way it has been proposed to apply blue-fluorescent substances to coloured fabrics for the purpose of intensifying, refreshing or brightening the colour.

It has been proposed to use certain blue-fluorescent compounds to improve the purity or brilliance of the white pattern produced in methods of discharge and resist printing on textiles, by treating the textile at any suitable stage during the printing process with a blueefluorescent compound, so that the whiteness of the white part of the pattern is enhanced.

It has also been proposed to use blue-fluorescent substances in admixture with a blueing agent, to give an enhanced whiteningeffect.

- when viewed in ordinary light and another when illuminated by ultra-violet light.

It is also known to incorporate blue-fluorescent substances in textile-marking inks, which when applied in the form of an identification mark to articles to be laundered, will after the completion of the laundering operation, be normally invisible, but when viewed under ultraviolet rays will be brilliantly fluorescent and clearly legible.

Blue-fluorescent substances proposed for use for the above purposes comprise a great number of different organic compounds.

For some purposes it is essential or desirable thatthe blue-fluorescent substances should have a strong ailinity for the material to which they are applied, so that they are not removed when the materials are subsequently rinsed or washed or otherwise treated in aqueous liquids, and numerous blue-fluorescent compounds substantive to textile fibres have been described in the prior art for various industrial applications. Among the compounds proposed as substantive t'o cellulose are certain di-benzoylamino-stilbene sulphonic acids and substitution derivatives thereof, in particular diamino. derivatives such as, for example 4:4'- di p-aminobenzoylamino stilbene- 2 :2-disulphonic acid, or salts thereof.

Other substances consist of stilbene derivatives containing 1:3:5-triazine rings; compounds containing imidazole rings have also been proposed.

The present invention is based on the discovery of new chemical compounds which are substantive and impart fluorescent elTects to materials such as textiles or paper; which effects have good stability, not only to air and light, but also to sodium hypochlorite and similar bleaching agents; and the said compounds are therefore particularly useful for imparting fluorescent effects to materials which may be subjected to treatment with hypochlorite or the like. Such treatments are used, for example, in the bleaching of textiles or in the laundering of white articles for improving the colour or removing fruit, tea, coffee and similar stains which are not removed by the normal washing process.

The invention comprises a method of impart- 1 Preparation of Compound A.-4:4='-diaminoing to materials, particularly cotton, linen, rayon stilbene-2:2-disulfonic acid (23 g.; 0.062 mol) and other cellulose materials, blue fluorescent was stirred and heated with water (150 cc.) and effects by incorporating in the said materials a sodium carbonate (5 g.). When the solution small proportion of a new compound as described 5 boiled, more sodium carbonate was added until hereinafter. The invention also provides prepathe mixture became alkaline. Anisyl chloride rations comprising substances such as detergents, (21 g.; 0.124 mol) in pyridine (50 cc.; analytical starch and other substances, and containing reagent grade) was added during a period of a small proportions of the said new compound. In few minutes and the mixture heated under readdition, e invention provides methods of flux for one hour. The liquid was made alkaline eorporating the w compounds in textiles and once more with sodium carbonate and cooled. the like materials, e. g., in the presence of a de- The product was collected by filtration, and tergent. washed with water until it was a pale orange The incorporation of the compounds in textiles colour. a te articles y be Carried u y i The material was dissolved in hot aqueous pyrimersing the articles in an aqueous solution of dine (80:20; 2.5 litres), decolorised and filtered. the Compound It is found, however, that incor- On cooling the solution the product was obtained poration is often materially assisted by the presas a pale yellow crystalline powder. This was ence of small percentages (usually quantities be thoroughly washed with hot water and dried. low 1% are sui'licient) of electrolytes such as so- Yield, 14 g. (approximately 35%). dium carbonate, sodium sulfate or sodium chlo- Preparation of Compound -C.An essential preride. The process of the invention may advanliminary to thepreparation of this compound was tageously be applied to textiles in any stage of the synthesis of the necessary acyl chloride, viz. their manufacture or subsequently, that is to say p-ethoxybenzoyl chloride. to the yarn, to the newly woven fabric, to new Stage (a) .p-Etho:rybenzoic acid. p Hyarticles made therefrom, or in the washing or droxybenzoic acid (14 g.) was dissolved in sodium rinsing of such articles including soiled articles. hydroxide solution (8 g. in 100 cc. water). To the As the compounds are substantive to cellulosic cooled solution, diethyl'sulfate (30.8 g. or 27 cc.) textile fibres, the whitening efiect produced is of was added and then sufficient alcohol (60 cc.) a more or less permanent nature and will survive 30 to make the mixture homogeneous. It was almany ordinary washing or rinsing treatments. lowed to stand for three days, after which a The following substances are illustrative of slightly acidified test portion of the reaction mixpreferred embodiments for imparting blue fluoture gave no coloration with ferric chloride solurescence in accordance with the invention: tion. Suificient strong sodium hydroxide solu- Compound A.Sodium 4:4'-di-p-methoxybention was added to give a strongly alkaline reaction zoylaminostilbene-Z:2-disulfonate: and the mixture was heated under reflux for /2 AO Na O Na Compound B.-The ortho-compound correhour, after which it was'cooled and acidified. The

' crude dry product was recrystallized from bensponding to Compound A: 1

zene-a cohol :50 mixture; approximately 3 cc.) and gave shiny plates, M. P. 198 0.; yield,

0on3 some SOgNa 00113 11 Stage (b) .--p-Etho:cybenz0yl chZOTide.--p-Eth- Compound C.Sod1um 4:4d1-p-ethoxybenzoylaminostilbene zzzudisulfonatez oxybenzoic acid (4 g.) prepared as above was some ame Compound D.-Sodium 4 4' -di-4=' -methoxy- 3"-methylbenzoylaminostilbene -.2:2' disulfonate:

CHaOOCONHQCH=CHQNHCOOO CH3 V l v I OsNa CH3 SOIiNa CH3 7 Compound E.--Sodium 4:4'-di-3-acety1amimoved and the residue, which rapidly solidified no-4,-methoxybenzoylaminostilbene 2 2' diwhile still hot, was kept over caustic soda to remove traces of thionyl chloride. Without further heated under reflux with thionyl chloride (4 g.) in benzene (20 cc.) until there. was no further loss of hydrogen chloride. The benzene was resulfonate: I ongo o ONHQCH=CHNHC 0G0 CH3 l vnooom OzNa sloaNa l inooom Compound F.-Sodium NzN -bis- (3' -4 "di-. purification the product was used in the next g l f l e i 4:4I d1am1nostl1bene 2 .2 i s tzge (c) .-C'ompound C'.-4 4 -diaminostilomoOoonnOoiwonQnHooOo on )011; oaNa oaNa ()CH;

bene-disulfonic'acid (4 g.) in water (64 cc.) was Preparation of the foregoing compounds is il-' just neutrahzed at the boil with sodium carbonlustrated by the following:

ate. To the hot solution, -eth'oxybenzoyl ehleride (4.4 g.) in pyridine cc.)- was added all at once. The product was worked up in the usual fashion and finally crystallized from aqueous pyridine. It was obtained as a pale yellow microcrystalline powder. Yield 2 g. (30%).

The other compounds may be prepared in an analogous manner, using the appropriately substituted benzoyl chloride; i. e., for Compound B, the orthomethoxybenzoylchloride, for Compound D, the paramethoxy-meta-methylben2oylchloride, for Compound E, the para-methoxy-metanitrobenzoylchloride (with reduction and acetylation of the resulting compound), and Compound F, the meta-para-dimethoxybenzoylchloride.

, The following examples illustrate various applic'a'tions of the invention. The particular compound used for imparting blue-fluorescent effects to the materials treated in these examples was the sodium salt of 4:4-di-p-methoxybenzoylaminostilbene-Z:2-disulfonic acid (Compound A).

Undyed bleached cotton yarn was treated in an aqueous bath containing 0.14% of sodium sulfate and 0.005% of the blue-fluorescent compound. The treated yarn after rinsing and drying had a brilliant white appearance in daylight, and showed strong blue fluorescence when illuminated by ultra-violet light and remained strongly fluorescent after long exposure to daylight and ultraviolet light.

EXAMPLE II A new white cotton cloth was rinsed for a few minutes in an aqueous bath containing 0.005% of the blue-fiuoroescent compound. The treated cloth after drying and ironing showed a brilliant white appearance in daylight, which was not affected when the cloth was subsequently treated with a dilute solution of hypochlorite.

EXAMPLE III A white cotton cloth was washed in a wash liquor containing 0.6% by weight of a soap powder itself containing 0.015% by weight of the blue fluorescent compound. After rinsing, drying and ironing, the cloth showed a blue fluorescence when illuminated by ultra-violet light and a brilliant white appearance when illuminated by day'- light.

All the foregoing compounds have been tested in the foregoing manner and give satisfactory results. Good results are also obtained in washing soiled cotton cloths with a wash liquid containing soap powder and the blue-fluorescent compound, in a manner similar to the foregoing; even in the first washing, and the effect improves with subsequent washings.

The requisite amounts of aminostilbene compounds in the washing liquor or in the prelim inary laundering treatment may vary within wide limits. In general, it is preferred to express this in terms of the amount of textile to be treated, and usually not over about 0.01% is necessary, based on the dry weight of the textile material to be washed. Proportions ranging from 0.025 to 0.000l% have been found suflicient to impart an appreciable whitening effect. There is no ad'- vantage in using more than is necessary to obtain the white effect and, of course, the amounts used should be less than sufiicient to impart a colored effect thereto. The amount need not be larger than 0.05%, based on the textile materialto achieve a satisfactory whitening effect.

6 However, since the use of excessive quantities of blueefl'uorescent substances does not in general produce over-blueing, which is an objectionable feature of the commonly used blueing agents, higher amounts, say up to one per cent or more, may be used without detriment to the effect produced. Such higher amounts, however, usually'serve no useful purpose once the quantity producing maximum whitening effect for a given case has been reached.

If the detergent composition contains 0.01 to 0.075% by weight of the aminostilbene compound and the washing liquor contains 0.25 to 0.75% by weight of the detergent composition, the concentration in the liquor of the aminostilbene compound can be readily calculated.

'The compounds of the present invention are particularly suitable for use in starch preparations for imparting fluorescent effects to materials such as textiles and the like.

EXAMPLE; IV

A solution was preparedcontaining 200 cc. of

water, 0.01 g. of the blue-fluorescent compound I used in the preceding examples and 1 g. of sodium sulfate. 20 g. of good quality maize starch was suspended in this solution at 40 C. for 30 minutes, filtered off and dried at 40 C. The treated starch was very much whiter than the original starch. An improvement in the whiteness of starch was also obtained by using only one-tenth of the above quantity of the compound in a similar manner. I

A starch whitened in the above manner was found capable of imparting a whitening effect to textile materials when used to starch the materials according to usual domestic laundering practice. For such laundering purposes, it is found that the starch would preferably be treated in the above manner with from 0.03% to 0.3% of the compound calculated on the weight of the starch.

EXAMPLE V A new white cotton cloth was treated with an aqueous solution containing 0.01% of the bluefluorescent substance used in the preceding examples and 0.004% of ultramarine. A brilliant white appearance was imparted to the cloth,

which was considered by some observers to be preferable in tone to that obtained by the use of the blue-fiuoroescent substance alone.

It will be realized that a preparation can be made, in accordance with the invention, com-'- prising a blue-fluorescent substance of the general formula mentioned above, and a blueing agent, that is a blue-coloured substance such as is used in the normal blueing treatment for washed textile articles. Such a preparation may also contain starch, and any fillers and other substances such as are incorporated in blueing agents.

In this connection, 'it may be mentioned that to a certain extent whiteness is a subjective impression of the observer. Shades of white exist, for example a bluish white, a greenish white or a pinkish white; and while one observer may consider a bluish white to be the whiter of samples of the three shades, another observer may prefer the greener shade. The incorporation of a small amount of coloured substance with the blue-fluorescent compound enables any desired shade of white to be given to the material to which the blue-fluorescence is imparted, and any suitable coloured substance or dye may be so in- I corporated. Thus the mixture of a blue-fluorescent substance and a suitable dye or pigment in the requisite proportions, together with any filling agents may be formed into a useful preparation for the purposes of the invention.

EXANDPLE VI A transparent sheet of regenerated cellulose of the type commercially used as wrapping material was immersed in an aqueous bath containing 0.1% of the blue-fluorescent compound dissolved in a liquid consisting of 94 parts water and 6 parts glycerine. The sheet after drying possessed the property of absorbing ultra-violet light and this property was not noticeably impaired by prolonged exposure of the sheet to air and light. Transparent sheet material treated in this way can therefore be used with advantage for wrapping foodstuffs or other commodities which are sensitive to light and which are kept in storage or exhibited on shop counters or in shop windows for long periods of time.

The compounds of the present invention may usefully be incorporated in detergents, in any form such as bars, tablets, powders, flakes. The incorporation in soap powder has already been mentioned above in Example III. In this way a detergent is provided which simultaneously washes and whitens materials to which it is applied.

The detergents that are used with the stilbene compound are of the kind suitable for and customarily used in textile laundry practice. Suitable detergents generally are of the organic detergent type. Soaps form one large group of organic detergents. Another large group of organic detergents consists of surface-active compounds which consist of a combination of a hy- CH O drophylic group with a lipophilic group which may be any fairly long chain (usually aliphatic but sometimes mixed aliphatic-aromatic), with or without unsaturated or substituted groups. These include sulfonated oils such as the Turkey red oil of commerce, alkyl sulfates such as sodium lauryl sulfate (Gardinol); aliphatic sulfonates such as the condensation product of oleoyl chloride with the sodium salt if isethionic acid (Igepon A), the condensation product of oleoyl chloride with the sodium salt of taurine (Igepon T), diainyl sodium sulfosuccinate, alkyl aryl sulfonates such as the sodium salt of an alkyl benzene or naphthalene sulfonate acid wherein the alkyl group contains about 8 to 18 carbon atoms (Nacconol), Twitchell reagents, quaternary ammonium compounds such as cetyl trimethyl ammonium chloride, partial esters of polyhydric alcohols, such as mono stearin sodium sulfo acetate, sodium glyceryl monolaurate sulfate (Syntex M), dioctyl sodium sulfosuccinate (Aerosol OT), sapamines, pentaerythritol monostearate (Pentamul 6) polyglycol esters, and the like (as are known in the art, for instance, Bailey, Industrial Oil and Fat Products, Interscience Publishers, Inc., New York, N. Y., 1945, chapter XII; and Dean, Utilization of Fats, Chemical Publishing Company of New York, Inc., New York, N. Y., 1938, chapter IX, part While the above described compounds are included as illustrative embodiments of a preferred mode of practicing the invention, other compounds are those of the general formula in which each R and R1 is a hydrocarbon radical, such as alkyl, aryl, or aralkyl, lower alkyl of from 1 to 4 carbon atoms being preferred; each x and in being zero or a small integer such as 1, 2 or 3, or the like; each n, m, m and 1111 being integers expressing the number of the respective groups substituted in the respective benzene rings, such as 1, 2, 3, and the like (the maximum number being the positions on the benzene rings which are not otherwise substituted) each B being hydrogen or a cation such as sodium, potassium, ammonium, or the like; and each A and A1 being hydrogen or a substituent such as methyl, acetylamino, and the like groups; but the compounds must not contain any free (primary) amino groups directly attached to any benzene ring, since the presence of such groups renders the compounds unstable to light, air and oxygen. Any of the benzene rings may contain substituents (except as specified above), such as methyl, acetylamino, and the like. Salts, such as sodium salt, are most convenient to use in practice.

A typical compound wherein m is 3 and m1 is 3 is the following:

Sodium 4 4'-di-3 '14 '5 -trimethoxybenzoylaminostilbene-2 2 -disulfonate:

ooh, CH=OHNHCOC O on,

A I OQNa OsNfl 0 CH3 CHONELCOONECOOO OH;

so'ma CHONHCO OsNa The other compounds within the broad formula may likewise be prepared using analogous reagents containing the appropriate substituents.

In the textile industry the compounds have use in their application to piece goods, yarns, fibre, fabrics and articles such as shirts, towels, sheets and the like made therefrom. Such materials may be treated with a dilute aqueous solution of the substance, which becomes attached to the material, giving it a brilliant white appearance, which, owing to the substantive properties of the substance, will remain through many normal washing and rinsing operations, thus removing the necessity for special blueing or whitening treatments each time the material is laundered.

Amongother useful applications of the inven- NH. C O 0 CH3 2,643,197. 9' a 10 tion maybe mentioned the preparation of fluoresdetergent; comprising an organic detergent and cent inks for marking textile fabrics'to be cleaned not more than about 0.075% by weight of the or laundered with identification marks whichare compound of claim 3.

normally invisible but strongly fluorescent in ul- 10. A composition consisting essentially of a tra-violet light. It is clearly essential that such detergent comprising an organic detergent and identification marks. Withstand customary launnot more than about 0.075% by weight of the dering treatments and in. particular do not becompound of claim 4..

come discolored when, for example,'hypochlorite 11. A composition consisting essentially of a is used in the wash or the fabrics are dried in the detergent comprising an organic detergent and sun, since any discoloration would obviously be w'not more than about 0.075% by weight of the highly detrimental. Identification marks procompound of claim 5..

duced by means of the blue-fluorescent com- 12. A composition consisting'essentially of a pounds according to the invention remain pracdetergent comprising an organic detergent and tically unafiected by normal laundering operanot. more than about 0.075% by weight of the tions. compound. of claim 6..

The invention is not limited tothe applica- 13. A method of laundering textile material tions specifically referred to in this specification, which comprises wa'shihg' said material with an but is useful for any purpose to whichlight-stable, aqueous solution comprising water and a deterblue-fluorescent substances may be applied, exgent composition consisting essentially of a deteroept as is not within the scope of the appended 2o gent comprising an organic detergent and about claims. 0.01% to about 0.075% 'by weight of a compound We claim: of claim 1.

1. A compound of the formula 14. A method of laundering textile material A which comprises washing said material with an CH NH OONH CO aqueous solution comprising Water and a detergent composition consisting essentially of a deter- SOaB (03)", gent comprising an organic detergent and about 0.01% to about 0.075% by weight of a compound A of claim 2. 15. A method of laundering textile material SOBB RM which comprises washing said material with an aqueous solution comprising water and a deter- Yvhere each B Is miamber of h groupd conslst' gent composition consisting essentially of a deteri of hydrogen sodlpm potassmm an ammogent comprising an organic detergent and about mum, where each a: is selected from the group 0 01% to about 0 0757 by Weight of a com ound consisting of 0 and 1, where each A is a member o p of the group consisting of hydrogen, methyl and of 01mm acetylamino, Where each R is an alkyl radical of A metrilod of 1a}1nderi ng textiie material 1 to 4 carbon atoms, and Where each m is an WhlCh comprises washing said material with an teger selected from the group consisting of 1, 2 40 aqueous Solution Comprising W te and a deterd 3, gent composition consisting essentially of a deter- 2. A compound of the formula, gent comprising an organic detergent and about CH3OC OONHOH=CHNHODODGE;

some some 3. A compound of the formula: 0.01% to about 0.075% by weight of a compound of claim 4. CONH CH=CHONHCO 17. A method of laundering textile material CH which comprises washing said material with an OCHK soaNa OaNa O 3 aqueous solution comprising water and a deter- 4. A compound of the formula: gent composition consisting essentially of a deter- C2115OCONHCH=CHC NHCOC OC2115 AOQNa S O3Na 5. A compound of the formula:

CH3 some 6. A compound of the formula:

l l l NHCOCH; SO Na some NHOOCHa 7. A composition consisting essentially of a detergent comprising an organic detergent and gent comprlsmg an organic detergent and about not more than about 0.075% by weight of a com- 0.01 to about 0.075% by weight of a compound pound of claim 1. of claim 5.

8. A composition consisting essentially of a 18. A method of laundering textile material detergent comprising an organic detergent and which comprises washing said material with an not more than about 0.075% by weight of the aqueous solution comprising water and a detercompound of claim 2. gent composition consisting essentially of a deter- 9. A composition consisting essentially of a gent comprising an organic detergent and about References Cited in the file of this patent UNITED STATES PATENTS Name Date Holste Apr. 22, 1913 Paine Aug. 10, 1937 Number Number Number Name Date Eggert Aug. 29, 1939 Schmid Apr. 2, 1940 Axelrad Feb. 8, 1944 Tainsh July 29, 1947 Lacey Feb. 17, 1948 FOREIGN PATENTS Country Date Great Britain 1911 Great Britain Sept. 17, 1937 Great Britain June 24, 1940 Great Britain 1947 France Mar. 22, 1943 Germany 1912 Norway 1914 Switzerland 1912 OTHER REFERENCES To Serial No. 381,856, Wendt (A. P. C.), published May 11, 1943.

Claims (2)

1. A COMPOUND OF THE FORMULA

7. A COMPOSITION CONSISTING ESSENTIALLY OF A DETERGENT COMPRISING AN ORGANIC DETERGENT AND NOT MORE THAN ABOUT 0.075% BY WEIGHT OF A COMPOUND OF CLAIM 1.