US2643198A - Fluorescent compound and methods of imparting fluorescent effects to materials - Google Patents

Description

Patented June 23, v 1953 FLUORESCENT-y COMPOUND AND METHODS OF IMPARTING FLUORESCENT EFFECTS TO MATERIALS Leslie Noel Savidge and Richard Thomas, Bromborough, England, assignors to Lever Brothers Company, Cambridge,

Maine Mass., a corporation of No Drawing. Original application March 30,

1948, Serial No. 18,066. Divided and this application August 13, 1949, Serial No. 110,223. In Great Britain April 3, l94-7 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, 1 textiles, with fluorescent substances which, without substantially altering the color. 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 light in the violet end of the spectrum is re-emitted within the blue portion of the spectrum.

a The present invention is based on the discovery of new chemical compounds which are substantive and which impart fluorescent effects to materials,such as textiles; 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 16 Claims. (c1. iii-33.5)

new articles made therefrom, or in the washing or rinsing of such articles including soiled articles. As the compounds are substantive to cellulosictextile fibres, the whitening effect produced is of a more or less permanent nature and will survive-many ordinary washing or rinsing treatment with hypochlorite or the like. I Such treatments are used, for example, .in the bleaching of textiles or in the laundering of white articles for improving a the color or removing fruit, tea, coffee and similarstains which are not 'removed by the normal washing process.

The invention comprises a method'of imparting to materials, particularly cotton, linen, rayon and other cellulose materials, blue fluorescent effects by incorporating in the said materials: a small proportion of a new compound as described; hereinafter. The invention also provides preparations comprising substances such as detergents, starch and other substances and' containing small proportions of the said new compound. In addition, the invention provides'methods of in'-' corporating thenew' compoundsin textilesan'd the like materials, e. g.,- in the presence of a detergent.

The incorporation of the compounds in textiles and textile articles may be carried out by im"- mersing the articles in an aqueous solution of the compound. It is found, however, that in corporation is often materially 'assisted 'by the presence of small percentages (usually quantities below 1% are sufficient) of electrolytes such as sodium carbonate, sodium sulfate or sodium chloride. The process of the invention may ad.-' vantageously be applied to textiles in any stage of their manufacture or subsequently, that is to' say to the yarn, to the newly woven fabric, to

treatments.

The substances which are employed in accordance with the invention have the following 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 :0 and am being zero or a small integer such as 1, 2v or 3, or the like; each n, m being integers expressing the number of the respective groups substituted in the benzene rings, such as l, 2, 3, and the like (the maximum number being the positions on the benzene rings which are not otherwise substituted) each 172, m1 being integers expressing the number of groups substituted in the terminal benzene rings, such number being at least 2 and not more than the number of positions on the benzene rings which are not otherwise substituted; B being hydrogen or a cation such as sodium, potassium, ammonium, or the like. The compounds should 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 siibstituents (except as specified above), such as methyl, acetylamino, and the like.' Salts, such as sodium salt," are most convenient to use in practice.

In a preferred embodiment the compounds have the formula (0 R)2 or 3 CH NHCO 0,11 GHQ-b11300 (0 1): or a ing compounds are illustrative:

3 COMPOUND No. 1

Sodium N :N-bis-(3-4-dimethoxybenzoyl) 4:4-

diaminostiZbene-Z:2-disulfonate orno c OHNQOH=C HONHC G0 om 6on3 SO Na some 0 on.

COMPOUND NO. 2

Sodium N :N '-bis- (3 :4:5-trz'methoa:ybenzoyl) 4 :4 -diaminostilbene-2 :2 -disul,f.onate CH3? con. CHaO CONH CH=CH NHCO 0cm Any of the above compounds may be prepared by reacting 4 :4-diaminostilbene-2 2'-disulfonic acid with the corresponding acyl chloride and in the presence of suflicient sodium carbonate to render the mixture alkaline. For instance, in the case of Compound No. 1, meta-para-di-methoxybenzoyl-chloride in pyridine is added during a period of a few minutes and the mixture heated under reflux for one hour. The mixture is heated once again with sodium carbonate and cooled. The product was collected by filtration and washed with water. The material may be purified by dissolving in hot aqueous pyridine, decolorized and filtered. On cooling the product crystallized which can be washed with water and dried.

Compound No. 2 can be prepared in a similar manner except that 3,4,5-tri-methoxybenzoyl chloride is used as the reagent for introducing the appropriately substituted benzoyl group.

The following examples illustrate the invention and are applicable to any of the compounds described.

EXAMPLE I Undyed bleached cotton yarn is 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 has 8.

brilliant white appearance in daylight, and shows strong blue fluorescence when illuminated by ultra-violet light and remains strongly fluorescent after long exposure to daylight and ultra-violet light.

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

EXAMPLE III ing 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 preliminary 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 0.001% have been found sufllcient to impart an appreciable whitened eil'ect. There is no advantage in using more than is necessary to obtain the white effect and, of course, the amounts used should be less than sufllcient to impart a colored efiect thereto. The amount need not be larger than 0.05%, based on the textile material to achieve a satisfactory whitening efiect. Higher amounts 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 containing 200 cc. of water, 0.01 g. of the blue-fluorescent compound, '1 g. of sodium sulfate, and 20 g. of good quality maize starch-is suspended in solution at 40 C. for 30 minutes, filtered ofi and dried at 40 C. The treated starch is very much whiter than the original starch. An improvement in the whiteness of starch is also obtained by using only onetenth of the above quantity of the compound in EXAMPLE V A new white cotton cloth is treated with an aqueous solution containing 0.01% of the bluefluorescent substance and 0.004% of ultramarine. A brilliant white appearance is imparted to the cloth, which is considered by some observers to be preferable in tone to that obtained by the use of the blue-fluorescent substance alone.

It will be realized that a preparation can be made, in accordance with the invention, comprising a blue-fluorescent substance of the general formula mentioned above, and a blueing agent, that is a blue-colored 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 colored 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 colored substance or dye may be so incorporated.

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.

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 such as the Turkey red oil of commerce, alkylv sulphates such as sodium lauryl sulfate (Gardin01) aliphatic sulfonates such as the condensation product of oleoyl chloride with the sodium compound are of the kind suitable for and cus- Q O Q sation product of oleoyl chloride with the sodium salt of taurine (Igepon T), diamyl 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 5) 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.

Among other useful applications of the invention may be mentioned the preparation of fluorescent inks for marking textile fabrics to be cleaned or laundered with identification marks which are normally invisible but strongly fluorescent in ultra-violet light. It is clearly essential that such identification marks withstand customary laundering treatments and in particular do not become discolered when, for example, hypochlorite is used in the wash or the fabrics are dried in the sun, since any discoloration would obviously be highly detrimental. Identification marks produced by means of the blue-fluorescent compounds according to the invention remain practically unaffected by normal laundering operations.

The invention is not limited to the applications specifically referred to in this specification, but is useful for any purpose to which light-stable blue-fluorescent substances may be applied, except as is not within the scope of the appended claims.

This application is a division of our application Serial No. 18,066 filed March 30, 1948.

We claim:

1. A compound of the general formula 2. A compound of the formula:

I OR

BOaNa in which R is an alkyl radical having 1 to 4 salt of isethionic acid (Igepon A), the condencarbon atoms.

son;

in which B is selected from the group consisting of hydrogen, sodium, potassium and ammonium; and R is an alkyl radical having one to four carbon atoms.

4,4,4; bis (3,4 dimethoxy benzoylamino) -stilbene-2,2-disodium sulfonate.

5. A method of laundering textile material which comprises washing said materials with an aqueous solution comprising water and a detergent composition consisting essentially of a detergent comprising an organic detergent and about 0.01% to about 0.075% by weight of a compound of claim 3.

6. A method of laundering textile material which comprises Washing said materials with an aqueous solution comprising water and a detergent composition consisting essentially of a detergent comprising an organic detergent and about 0.01% to about 0.075% by Weight of acompound of claim 2.

7. A method of laundering textile material which comprises washing said materials with an aqueous solution comprising Water and a detergent composition consisting essentially of a detergent comprising an organic detergent and about 0.01% to about 0.075% by weight of a compound of claim 1.

8. 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 3.

9. A composition consisting essentially of aby weight of a- 11. A composition :consisting essentially of an organic detergent comprising a soap and not more than about 0.075% by weight of a compound of claim 1.

12. A composition consisting essentially of-an organic detergent comprising a synthetic organic nonsoap detergent and not more than about 0.075% by weight of a compound of claim 1.

13. A method of imparting blue-fluorescent effects to materials which comprises immersing said materialsin an aqueous'solution containing from about 0.0001 to about 0.05% by weight, calculated on the basis of the dry weight of materials treated, of a compound of claim 3, removing said materials from said solution and'drying said materials.

14. The method of claim 13 in which the material treated is a fibrous cellulosic material.

15. Fibrous cellulosic material having incorporated therein about 0.0001% to about 0.05% by weight of a compound of claim 3. 1

16. Fibrous cellulosic material having incorporated therein about 0.0001% to about 0.05% by Weight of a compound of claim 1. I Y

LESLIE NOEL SAVIDGE. RICHARD THOMAS.

.References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Serial No. 381,856 (A. P. c. 11,1943.

published May 7

Claims (2)

1. A COMPOUND OF THE GENERAL FORMULA

16. FIBROUS CELLULOSIC MATERIAL HAVING INCORPORATED THEREIN ABOUT 0.0001% TO ABUTT 0.05% BY WEIGHT OF A COMPOUND OF CLAIM 1.