US3509049A

US3509049A - Fabric softening and brightening compositions

Info

Publication number: US3509049A
Application number: US507998A
Authority: US
Inventors: Reinhard Zweidler
Original assignee: Geigy Chemical Corp
Current assignee: Novartis Corp
Priority date: 1965-11-01
Filing date: 1965-11-01
Publication date: 1970-04-28
Anticipated expiration: 1987-04-28

Description

United States Patent 3,509,049 FABRIC SOFTENING AND BRIGHTENING COMPOSITIONS Reinhard Zweidler, Basel, Switzerland, assignor to Geigy Chemical Corporation, Greenburgh, N.Y., a corporation of Delaware No Drawing. Filed Nov. 1, 1965, Ser. No. 507,998 Int. Cl. D06m 13/46; C09k l/02 U.S. Cl. 2528.75 7 Claims ABSTRACT OF THE DISCLOSURE Detailed disclosure This invention relates to novel fabric softening and brightening compositions which are useful especially for the simultaneous brightening and softening of the handle of textile fabrics and the like textile fiber materials, especially of cellulosic fiber materials such as cotton or polyamide fibers such as nylon or wool. More particularly, in a first aspect, the present invention relates to fabric softening and brightening agents for household use in the softening and simultaneous brightening of cellulose, especially cotton fabrics.

Nowadays, a great many home laundry softeners contain optical brighteners. Addition of such brighteners increases the appeal of these products, which are usually supplied in the form of thick pastes to be dispensed from plastic pressure tubes and the like dispensers. These thick pastes are then diluted with Water and form stable dilute aqueous dispersions which are highly suitable for home laundry. Use of these agents imparts a soft handle to the treated fabrics, and brightens them; moreover, depending on further adjuvants in these agents, additional advantages may be gained by treating fabrics with them, e.g. elimination of static electricity, easier drying and ironing, and others.

Brighteners are also included in softeners because detergent brighteners are partially quenched on the fabric by the brightener-free softeners. A 10-30% loss in brightness may thus be caused, depending on fluorescence level of the fabrics. Quenching is usually manifested as a dulling effect. However laundry washed with brightenercontaining detergent is given a full, brilliant brightened aspect if rinsed with brightener-containing softener immediately after the washing.

Main ingredients of fabric softener compositions for household use are active quaternary compounds among which especially di-(hydrogenated tallow) dimethyl ammonium chloride and similar substances, or ethoxylated dialkyl dimethyl ammonium sulfate and equivalent compounds, or imidazolinium derivatives have been recommended.

Of the large number of known cationic, nonionic and anionic optical brighteners, only a handful of anionic brighteners have hitherto been found useful for incorporation into softener-brightener compositions.

Many of the known optical brighteners are not sufficiently soluble, some discolor the softener formulation and thus make the aspect of the latter unappealing, some cause separation or precipitations in the formulation, and

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some are effective primarily on synthetic fibers, but not on natural fibers such as cotton.

The anionic brighteners which were found suitable for fabric softener application had to be highly soluble, compatible with the softener, and should not introduce free inorganic electrolyte into the formulation. A special advantage of anionic brighteners in softener formulations was seen to reside in formation of an ion complex with the cationic quaternary softener; solubility of the complex increases with solubility of the brightener. Free inorganic electrolyte was expected to lower solubility and, at high concentrations, even salt out the brightener.

The only brighteners hitherto recommended for use in softeners as satisfying the above requirements are anionic brighteners belonging to the class of bis-(triazinylamino -stilbene-disulfonic acids.

Contrary to these requirements of the known brightener-softener mixtures, novel fabric softener-brightener compositions according to the first aspect of the present invention consist essentially of an aqueous dispersion of:

(a) A fabric softener falling under the formula Rl Ra wherein R represents alkyl of from 10 to 24 carbon atoms,

each of R R R represents alkyl of from 1 to 24 carbon atoms, and

X represents an anion, preferably the anion of a noncolor-imparting acid, and

preferably R represents alkyl of 10 to 24 carbon atoms,

the content of the softener in each liter of the composition amounting to at least about 20 grams, and preferably 50 to grams.

(b) An oxacyanine optical brightener of the formula (c) Viscosity-adjusting additive, preferably electrolyte, such as weak organic acids, alkali metal or ammonium salts of the latter or similar electrolyte agents which influence the viscosity of thixotropic system; if viscosity coeflicients above that of water are desired, e.g. for reasons of storage, depending on the nature of the container and the method of dispensing chosen, the amount of component (c) should be sufiicient to impart to the entire composition a viscosity coefficient of at least about 2 centipoises. Viscosity coefficients in the range of 5 to 500 centipoises are preferred in composition for household use.

Furthermore, the compositions according to the invention may contain other smoothing agents, coloring agents, perfumes, emulsion stabilizers and antistatic agents; the balance of the composition consists of water.

Oxacyanine brighteners have been added in the past to quaternary salts of condensation products of formaldehyde with long chain fatty acid amides and the like substances useful as crease-proofing agents or water-proofing agents, in which solubility of the agents plays a secondary part or is even undesirable. Indeed, since the oxacyanine brighteners are poorly to very poorly soluble in water and practically insoluble in aromatic hydrocarbons, and, in the cold, in most other industrial solvents, they appeared to be very well suited for such known uses, While they were deemed unsuited for incorporation into fabric softeners.

As has been mentioned above, good solubility was deemed a paramount requirement for the latter.

The softener-'brightener compositions according to the invention, however, are distinguished by an unexpected excellent dispersibility in water, in spite of the slight to very slight solubility of the brightener component. Moreover, while the known crease-proofing compositions containing oxacyanine brighteners are not stable in aqueous medium, but form precipitate of the brightener after a few hours of storage, the novel brightener-softener compositions according to the invention show, very surprisingly, an excellent stability, and can be stored for months without separation of its components.

Application of the softener-brightener compositions according to the invention for rinsing detergent-washed household laundry especially of cellulose fiber fabrics such as cotton, gives the goods at blueish white shade which is fast to light and gives the goods an improved soft handle.

The aforesaid blue fluorescence with, at the same time, good fasteness to light is a further advantageous property, of the optical brightener-softener compositions according to the invention.

In Formula II defining the oxacyanine brightener component, R, R", R and R, represent, for example, the methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl group. Non-ionogenically substituted alkyl groups in the position of R and R have, as substituents, for example, a cyano group or halogen; examples are the B-cyanoethyl or a halogen alkyl group such as the fi-chloroethyl group.

The colorless anion X of the compounds of Formula II represents, for example, chloride, bromide or the equivalent of an inorganic or organic oxygen acid of hexavalent sulfur.

In particularly active compounds of Formula II which are valuable because of their pure white effects, R, R", R R are each the methyl group and X is the equivalent of the anion of an inorganic or organic oxygen acid of hexavalent sulfur, in particular the equivalent of a sulfate ion, methoor etho-sulfate ion, p-tolueneor benzenesulfonate ion.

In aqueous rinsing baths, the softener-brightener compositions are used in such concentration that the content of optical brightener of Formula II in the liquor is preferably about 0.003 to 0.25% calculated on the textile goods to be brightened and softened. The content of softener of Formula I is 0.1 to calculated on the weight of the goods.

According to a second aspect of this invention, there are provided softener-brightener compositions similar to those described hereinbefore, but in which the softener component of the mixture is of the formula wherein R, R and R" have the same meanings as in the preceding formulas each of the alkylene bridges has from 2 to 3 carbon atoms, and

Y represents one of the groupings wherein n represents an integer ranging from 1 to 20, and is preferably l to 3.

All details given with regard to the softener-brightener compositions under the first aspect of this invention apply equally to the compositions according to this second and to the following third aspect of the invention.

When applied in such concentration in the rinsing liquor that an amount of 0.1 to 5 grams of softener is deposited on every grams of fiber material, excellent softening and brightening effects are achieved with the softener-brightener mixture according to this aspect of the invention especially on natural polyamide fibers such as Wool, but also on acid acrylic fibers of the type coritaining sulfo and preferably also carboxyl groupslCourtelle and Orlon type acrylic fibers).

At the same time treatment with the softener-brightener compositions imparts to treated fabrics made from cellulosic fibers such as cotton, but also from various synthetic fibers such as polyamide, polyester or polyacrylonitrile fibers a very satisfactory antistatic finish without any undesirably quenching effect on the brightener component.

According to a third aspect of this invention, there are provided softener-brightener compositions similar to those described hereinbefore, but in which the softener component of the mixture is a colloidally dispersible 1,2- substituted imidazoline salt, preferred softeners of this class falling under the formula Ra Ra (IV) wherein X and R have the same meaning as in the preceding formulas,

R represents hydrogen or alkyl of from 1 to 18 carbon atoms,

R represents alkyl of from 1 to 18 carbon atoms,

hydroxy lower alkyl, higher fatty acyl-amino-lower alkyl and higher fatty acyl-oxy-lower alkyl, and

each of R and R represents hydrogen or alkyl of from 1 to 6 carbon atoms,

higher fatty acy representing the radical of a fatty acid of from about 9 to 19 carbon atoms.

Lower in connection with an aliphatic radical as used in this specification and the appended claims means that such radical has not more than 4 carbon atoms.

When textile fabrics and the like materials made from cellulosic fibers such as cotton or woolen materials or various synthetic fibers such as polyamide, polyester or polyacrylonitrile fibers are treated e.g. in the household Wash or in a single bath process with a rinsing liquor to which a softener-brightener composition according to this aspect of the invention has been added, these materials are simultaneously given a softened handle and an antistatic finish without the brightening efiect on the textile material being noticeably quenched thereby.

Treatment of the above-mentioned fiber materials with brightener-softener compositions according to the second and third aspect of the invention, preferably in the form of homogeneous, very stable aqueous dispersions, allows Wool and/ or cellulose fiber material such as cotton to be brightened and softened simultaneously with the finishing of other fibers, e.g. the treatment of synthetic fibers liable to accumulate static charges, with water soluble, cationactive agents acting as antistatics.

The content of the antistatic component in the treatment liquors should be sufficient to deposit on the fibers advantageously 0.5 to 50% calculated on weight of the textile material the handle of which is to be softened and/or which is to be rendered antistatic.

3,509,049 5 6 The high yield rates of both active Components present in the above example, 0.025 part of the brightening agent in the compositions according to all three aspects of the memloned are used Instead of (101 P invention, which are attained in the treatment of textile I when Example 1 is repeated, but the brightening agent used in the composition employed in that example is regoods therewith, 1.e. favorable ratio between amount of placed by equimolar parts of one of the compounds listed each Component dePOSIted 011 the fibers t the amount in Table I infra, fabrics having a similar white effect and in the liquor containing the composition also distinoft handl are tt i d guishes the latter from known fabric softener-brightener Example 3 compositions.

10 parts of wool flannel are treated for 10 minutes at a The th p of the f i are further inns 10 temperature of 40 in 300 parts of aqueous liquor contrated by the following non-limitative examples. taining 0.7 part of a softener of the formula CHZOCO 01511 7 CH3 013E370 O O CHz-IIIrCHzCH2N CHzCHz-N CH2C O O G gi-I 3C1 CH3 H3 CH1 Where not otherwise expressly stated, parts and perand 0.025 part of the brightening agent given in Example centages are given therein by weight. The temperatures 1. The material so treated has a strong White effect in dayare in degrees centigrade. The relationship of parts by light and has, in addition, a soft handle. weight to parts by volume is as that of grammes g.) to Similar results are otbained by treating 10 parts of cotminiliters 1 ton fabric in lieu of wool flannel by the procedure of Example 1 Example 3.

The brightener in Example 3 can be replaced by equimolar parts of the brightening agents given in Table I; woolen or cotton fabrics are then obtained having similar white effects and soft handle. Better antistatic properties are also imparted to these materials by using 1.0 to

10 parts of cotton cretonne are introduced into 300 parts of an aqueous liquor having a temperature of 35 and containing 0.5 part of the softening-brightening agent, produced as described below, which liquor is an aqueous dispersion of di-(hydrogenated tallow):dimethyl ammo- 1.8 parts of the softener in lieu of 0.7 Part. nium chloride and 3,3'-dimethyl-5, 5'-drmethoxy-oxacya- The fabric Softener used in Example 3 is produced as nine-p-toluene-sulfonate, and are lightly stirred therein follows: for 10 minutes. Thereupon, the cotton cretonne 1s re- 270 g of stearyl alcohol are heated to melting 104 g moved from the aqueous liquor and air-dried. The fabric of chloroacetic acid are added to the melt and i mix then shows a beautiful white effect and, in addition, has ture is heated at until no more Water distils a soft handle. off. This is the case after about 90 minutes. The reactive production f the ft bri ht r composition mass is then subjected to fractional distillation and the fraction boiling at 175 to 205 at 0.5 torr is isolated. It 86.7 g. of commercially available di-(hydrogenated talconsists of stearyl chloroacetate (yield rate about 93%).

low)-dimethyl ammonium chloride fabric softener con- 100 g. of this ester are heated to 50-60", 17 g. of pensisting of a mixture of tamethyldiethylenetriamine are added, and the whole is 18 parts of di-hexadecyl-dimethyl ammonium chloride, heated t0 a l-lt 85 on the water bath. An exothermic 56.25 parts of di-octadecyl-dimethyl ammonium chloride, action sets in which raises the temperature of the mix- 0.75 part of di-octadecenyl-dimethyl ammonium chloride, l about Aftel the reaction has abated, heat 3 pal-ts f isopropanop mg to about 90-95 is continued for 3 hours. 5 parts f Water and The mixture is stirred till, it becomes highly viscous 0.5 part of sodium chloride at COOhng and finally solidifies. 117 g. of the quaternary softenencompound of the formula given in Example 4 are heated with stirring at a temperature of -50, 2.0 45 are obtained.

g. of 3,3'dimethyl-5,5'-dimeth0xy-oxacyanine-p-toluene- 80 g. of the pulverized softener compound are insulfonate are added and the whole is stirred for 30 minrp rat into the softener-brightener composition as utes. The temperature is then raised to 55-60 and Warm described in p 1 in lieu of t e o tener used in water is added to make up a total weight of 1000 g. the atter composition.

A stronger brightening effect is obtained when using Exam 1 5.0 g. in lieu of 2.0 g. of the above br1ghtener 1n the p e 4 above composition. Similar results as in Example 3 are obtained when using an equivalent amount of the compound of the formula Example 2 CH3 on. 10 parts of cotton cretonne are treated for 15 minutes I at a temperature of 40 in 300 parts of an aqueous liquor CH OH 201- containing 0.6 part of bis-stearyl-bis-methyl ammonium 3 2 a chloride, and 0.01 part of the compound of the formula 000-018 37 OOOCIBHU i C-CH=O so CH 3 3 CHsO- \N/ -O-CH3 The aforesaid agents, as well as those mentioned in the is used instead of the softener used in Example 3, while following examples are introduced into the liquor in the following otherwise the same procedure as in that form of an aqueous mixed fabric softener-brightener comexample. position produced in a similar manner as described in The softener used in Example 4 is produced as folthe preceding examples. lows: 560 g. of chloro sulfonic acid are added dropwise After drying, the treated fabric has a beautiful white to 300 g. of triethylene glycol maintained by cooling at a effect and, in addition, has asoft handle. H5 temperature of 25-30. After the dropwise addition is A considerably stronger white shading is obtained if, complete, the temperature is raised to 40-45 and the viscous mixture is stirred at this temperature for one hour.

The mass is then passed through an inflow funnel having' a wide outlet tube into solution cooled to -10 which is prepared from 68 g. of caustic soda, dissolved in 1140 g. of aqueous 30% sodium hydroxide solution and the whole is stirred for one hour at the same temperature of 5-10. 709 g. of aqueous 40% dimethylarnine solution is added to the resulting paste and the mixture is then heated for 12 hours in an autoclave at a temperature of 170-175.

The contents of the autoclave are cooled to 40-45 and 300 g of caustic soda are added in the cold to the reaction mixture. After the entire caustic soda has been dissolved the oily upper layer formed is separated off and a further 100 g. of caustic soda are added thereto While heating mildly. When this caustic soda is dissolved the aqueous bottom layer is drawn off. During the separation of the base with the aid of caustic soda, a strong current of air is blown through the reaction mass, and excess dimethylamino thus set free is recovered by introduction of the air stream loaded therewith into water.

g. of animal charcoal are added to the oily upper layer, the mixture is then filtered and freed from residue dimethylamine by applying a water jet vacuum at room temperature. 335 g. of 88.6% tetramethyl-triethylenediamine (yield rate 72-73%) are thus obtained, 118 g. of tetramethyl-triethylene-diamine, are added to 346.5 g. of stearyl chloroacetate, at a temperature of 50-60". The mixture is then heated on a water bath. At a temperature of about 75 an exothermic reach sets in, whereby the temperature rises automatically to about 120"- 125, and the reaction mass becomes waxy. While cooling, it is stirred for as long as possible and is then left at a temperature of 9095 for 3 hours. After cooling to room temperature the completely solidified reaction mass is ground; 464 g. of the quaternary compound used as softener in Example 4 is obtained.

Example 5 10 parts of cotton cretonne are treated for minutes at a temperature of 40 in 300 parts of a liquor containing 0.3 part of 2-oleyl-l-alkyl-imidazoline acetate and 0.02 part of the brightening agent used in Example 1. The fabric so treated has a beautiful White effect, a soft handle and does not tend to accumulate static charges.

The brightening agent mentioned above can be replaced by equimolar parts of the compounds mentioned in Table I; similar white effects and a soft handle are then obtained, by following the same procedure as this example. (Alkyl in the above softener has from 15-17 carbon atoms.)

Example 6 Still softer handle and equally good, unquenched brightening effects are obtained when repeating Example 5, but using a softening composition containing per 1000 g. thereof 90 g. of l-methyl-l-(fl-stearoylamino-ethyl)-2- heptadecyl-imidazoline chloride and 3 g. of the brightening agent used in Example 1.

Example 7 10 parts of cotton cretonne are treated for 15 minutes at a temperature of 40 in 300 parts of a liquor containing 0.05 part of bis-stearyl-bis-methyl ammonium chloride, 0.3 part of 2-oleyl-l-rnethyl-imidazoline acetate and 0.02 part of the brightener used in Example 1. The fabric so treated has a strong White effect in daylight. In addition it has a soft handle.

The brightening agent given above can be replaced by equim-olar parts of the brightening agents given in Table I; the fabric treated as described in the above Example 4 then have a similar White effect and soft handle.

Example 8 Similar results as in Example 5 are also obtained when using in that example an equivalent amount of l-stearoylamino-ethyl-Z-heptadecyl-imidazoline lactate as softener component.

Example 9 10 parts of cotton poplin which have been given an anti-crease processing consisting of g. per liter of a reactive resin and 10 g. per liter of magnesium chloride, are treated at a temperature of 40 for 12 minutes in 300 parts of a liquor containing 0.04 part of bis-stearyl-bismethyl-ammonium chloride and 0.01 part of the brightener given in Example 1. The fabric sotreated has a beautiful white effect and, in addition, a soft handle. If, in the above example, 0.025 part of the brightening agent mentioned are used instead of 0.01 part, an equally soft handle and a considerably stronger white effect of the fabric is obtained.

The brightening agent mentioned above can be replaced by equimolar parts of the compounds given in Table I whereupon fabrics having a similar white effect and soft handle are obtained by following the procedure of Example 9.

Example 10 10 parts of cotton fabric are entered into 300 parts of a rinsing bath containing 0.6 part of bis-stearyl-bismethyl ammonium chloride, and 0.001 part of the brightening agent given in Example 1, and the goods are slightly moved therein for 15 minutes at a temperature of about 40. The cotton fabric is then removed from the rinsing bath and air-dried. The fabric has a beautiful brightening effect and a soft handle. When this cotton fabric is treated under the same conditions in other rinsing baths of the same composition, as is the practice in household washing, the white content of the fabric slowly increases and, with the concentrations given, a maximal brightening effect is attained after 16 consecutive rinsing baths. Determined on the Hunter scale for assessing whiteness, the white content increases as shown in the following table:

Times fabric was rinsed Degree of whiteness The effects obtained show a brilliant white shading. The amount of brightener mentioned in the above example can be changed within Wide margins. Rinsing baths containing from 0.0003 to 0.027 part of brightener can be used. The number of rinsing baths necessary to attain the maximal brightening effect is then correspondingly altered.

When Example 9 is repeated, but the softener by that used in Example 3, or if 0.01 or 1.5 part of the agent employed in Example 9 are used instead of 0.6 part if the temperature of the rinsing bath is 20 or 50 and the time of the fabric in the baths is 1 minute or 30 minutes, similar brightening effects and soft handle are obtained.

When Example 9 is repeated but rinsing baths are used which further contain 0.3 to 1 part of 3-oleyl-1-alkylimidazoline acetate and, in addition to cotton, also synthetic fibers such as polyamide, polyester or polyacrylonitrile fibers are treated in these baths, then the synthetic fibers are given an antistatic finish without the white effects on the cotton described above being noticeably quenched.

When Example 9 is repeated but the brightening agent used therein is replaced by equivalent amounts of one of the brighteners given in Table I, fabrics having similar White effects and soft handle are then obtained.

Example 11 20 parts of yarn of fibers made from polyacrylonitrile having a polymerization degree of about 35,000 and about 154 millimols of carboxyl groups per 100 g. thereof, but is free from sulfo group, yarn are given a pre-rinse at a temperature of 60 in 600 parts of water containing 0.6 part of non-ionogenic washing agent nonylphenol polyglycol ether having 8-15 ethyleneoxy groups, and 0.3 part of acetic acid and then the yarn is rinsed with water. The yarn is then introduced at 60 into an aqueous rinsing liquor containing 10 parts of a softening-brightening composition as described below, whereby 0.03 part of the compound of the formula 6H3 (IZHS and 0.9 part of 1-methyl-1-(fi-stearoylamino-ethyl)-2- heptadecyl-imidazoline chloride have been introduced thereinto. The liquor further contains 0.6 part of oxalic acid, 0.075 part of sodium metabisulphite and 0.15 part of a mixture of sodium tetrametaphosphate and sodium hexametaphosphate. The temperature of the liquor is raised within minutes to 9698 and kept for another minutes at this temperature. The yarn is then washed first with lukewarm and then with cold water and dried.

The yarn thus treated has a very beautiful white effect in daylight.

Similar brightening and softening effects are obtained if the brightener mentioned in the above example is replaced by an about equal amount of one of the brighteners listed in Table I below and if the softener used in this example is replaced by the same amount of one of the softeners listed in Table II below, and otherwise the procedure given in Example 11 is followed.

Example 12 Similar brightening and softening effects are obtained by repeating Example 11, but treating 20 parts of fabric consisting of polyacrylonitrile fibers having a polymerization degree of about 35,000 and 46 millimol of sulfonic acid groups and 17 millimol of carboxylic groups per 100 g. fiber weight, and otherwise following the procedure.

TABLE I The brighteners given in this table fall under the formula in which R, R", R R and X have the meanings given below:

No. R R R1 R2 X 1 CH3 on, on, on, OSO -Q 2 on; CH3 CH3 on, o s o2o1 a OH; on; on, on, 4 on, on on, on, 04);; 5 on, on, on, on3 s ol-o-on 6 OH; on, on: on, 0 s og--on 7 on, 011 ona CH3 0 s Q-on,

s on, CH3 CH3 CH3 OSOZQ a C2115 02H, on, on; 0 s Oz-Q-CH or under the formula V0 0 Y, o--on=o m t R1 R2 wherein R, R", R R Y and X have the meanings given below 10- CH3 on cm CH3 H osm-Q-om 11 CH3 CH3 on, on, on3 osm-Q-om TAB LE H CH3 CH3 9.8 g. of 2-methylmercapto-5-methoxybenzoxazole are dissolved in 36 g. of chlorobenzene while excluding moisture.

18.8 g. of methyl p-toluene sulfonate are added dropwise to the solution within one hour 'while keeping the mixture at -l30, and the whole is then stirred for one more hour under weak reflux. 8.2 g. of melted 2- methyl-S-methoxybenzoxazole are then added dropwise to the reaction mixture at -l40 Within 2 hours and, on completion of the addition, the whole is stirred for another two hours at this temperature. The reaction 1 1 mixture is allowed to cool to room temperature, 17 g. of water are added and the pH is adjusted to about 5.5 by the addition of an aqueous solution of about 2.5 g. of sodium hydroxide. The crude reaction product is filtered off and washed, first with chlorobenzene and then with water. The crude product is purified by stirring it at reflux temperature for minutes into a mixture of 22 g. of chlorobenzene and 16.5 g. of water the pH of which is about 5.5, cooling to and adjusting the pH to 7.5 with dilute sodium hydroxide solution. The pale yellow product is filtered 01f, washed with chlorobenzene and water and then dried under vacuum at 100-110. 3,3- dimethyl 5,5 '-dimethoxy-oxacyanine-p-toluene sulfonate is obtained as a yellowish powder which melts at 289- 291 with decomposition (M.P. uncorrected). The prodnot is an excellent agent for brightening cotton from rinsing baths in the presence of cation active compounds. It

can also be used for the brightening of nylon and, in acid baths, for the brightening of polyacrylonitrile fibers.

Example 14 CHaO 27.9 g. of 4-methoxy-2-amino-l-hydroxy-benzene are added to a mixture of 7.5 g. of glacial acetic acid and 21.6 g. of acetic acid anhydride at a temperature of 80-85 On completion of the addition, the whole is stirred for 6 hours at moderate reflux temperature whereupon first the acetic acid and the remaining acetic acid anhydride are distilled off under normal pressure and then the crude product is fractionated at 125-126/ 13 torr. To remove traces of adherent acid, the crude product is dissolved in an emulsion of xylene and water and the pH is adjusted to 7 with sodium carbonate. After removal of the aqueous phase, the xylene phase is first azeotropically dehydrated and the product is then redistilled in vacuo. 2-methyl-5- methoxybenzoxazole is obtained as an almost white crystalline mass which melts at 39-40" (uncorrected).

Example 15 A solution of 12.4 g. of potassium hydroxide in 30 g. of ethanol, having an initial temperature of 20 is added so slowly to a mixture of 20 g. of carbon disulfide and 20 g. of ethanol that the temperature never rises above 40. On completion of the reaction, 27.9 g. of 4-methoxy-2- amino-l-hydroxybenzene are added within 30 minutes, the whole is heated from 40 to 76 within 4 hours and then kept for one hour under weak reflux at about 76. g. of about 50-warm water are added to the reaction mixture in such a manner that the temperature of the mixure does not drop below and the excess of carbon disulfide and ethanol is then distilled off. When the distillation temperature has reached -97". another 27 g. of water are added to the mixture so that the temperature does no drop below 40-45 and the pH is adjusted to and maintained at a weak alkaline reaction to mimosa paper by the addition of sodium hydroxide solution. At the aforesaid temperature of 40-45 30.6 g. of dimethyl sulfate are added dropwise within 30 minutes and the whole is stirred for another 2 hours at 5-0-55 The mixture is then cooled to 20-25", 33.5 g. of xylene are added, stirring is continued for one hour and, after the addition of 1.0 g. of Hyfio the reaction mixture is filtered. After separating the two phases in the filtrate, the upper xylene phase is dehydrated by azeotropic distillation, the xylene is distilled off under ambient pressure and the reaction product is fractionated in vacuo at 167-169/ 13 torr. 2-methylmercapto-7-methoxybenzoxazole is obtained as a whitish crystal mass which melts at 55-57 (uncorrected).

Example 16 Example 17 This compound is produced analogously to Example 14 for the production of Z-methyl-S-methoxybenzoxazole except that 27.4 g. of 4,5-dimethyl-2-amino-1-hydroxybenzene are used instead of 27.9 g. of 4-methoxy-2-amino-lhydroxybenzene. 2,5 ,6-trimethylbenzoxazole thus obtained boils at a temperature of 139-142/ 15 torr, and solidifies to a white crystal mass.

Example 18 By using, in Example 13, 7.4 g. of 2-methylmercapto- S-methylbenzoxazole instead of 9.8 g. of Z-methylmercapto-5-methoxybenzoxazole and otherwise following the same procedure as described in Example 13, condensa tion with 18.8 g. of methyl p-toluene sulfonate and 8.2 g. of Z-methyl-S-rnethoxybenzoxazole under otherwise the same conditions, affords 3,3,5-trimethy1-S-methoxy-oxacyanine-p-toluene sulfonate in the form of a yellowish powder which melts at 261-263 with decomposition. The compound is a good agent for the brightening of cotton from rinsing baths in the presence of cation active compounds.

Example 19 This compound is produced analogously to Z-methylmercapto-S-methoxybenzoxazole by repeating Example 14, but using 246 g. of 4-methyl-2-amino-l-hydroxybenzene instead of 279 g. of 4-rnethoxy-2-amino-l-hydroxybenzene. Z-methylmercapto-S-methylbenzoxazole which is thereby obtained, boils at 149-l51/ 11 torr and solidifies to a white crystal mass which melts at 4243 (uncorrected).

We claim:

1. A fabric softening and brightening composition consisting essentially of (a) an aqueous base,

(b) a fabric softener falling under the formula R is alkyl of from 10 to 24 carbon atoms,

each of R R R is alkyl of from 1 to 24 carbon atoms, and X is chloride ion, the content of the softener in each liter of the composition amounting to at least about 20 grams;

() an oxacyanine optical brightener of the formula N+ is wherein Y represents hydrogen or methyl group,

R, R, R and R are methyl or ethyl groups,

X is chloride or bromide ions, the content of the brightener in the composition amounting per liter of the latter to about 0.3 to 8 grams.

2. A fabric-softening and brightening composition as described in claim 1, further comprising (c) a weak organic acid viscosity-adjusting additive in an amount sufficient to impart to the entire composition a viscosity of at least about 2 centipoises.

3. A fabric-softening and brightening composition as described in claim 1, wherein the content of said fabric softener in each liter of the composition amounts to about 50 to 80 grams.

4. A fabric-softening and brightening composition as described in claim 1, wherein the content of said optical brightener in each liter of said composition amounts to about 1 to 3 grams.

5. A fabric-softening and brightening composition as described in claim 1, wherein said fabric softener is di- (hydrogenated tallow) dimethyl ammonium chloride.

6. A fabric-softening and brightening composition consisting essentially of (a) an aqueous base,

(b) a fabric softener having the formula 14 wherein R is alkyl of from 10 to 24 carbon atoms, each of R R R is alkyl of from 1 to 24 carbon atoms, and X is chlorine, the content of the softener in each liter of the composition amounting to at least about 20 grams, and (c) an oxacyanine optical brightener having the formula COH=O c1130 -o-ona r f 1 CH3 CH3 0 wherein A represents an anionic equivalent selected from the group consisting of chloride, sulfate, monolower alkyl sulfate, phenylsulfonate and chlorophenyl-sulfonate. 7. A fabric-softening and brightening composition consisting essentially of (a) an aqueous base, (b) a fabric softener having the formula wherein R is alkyl of from 10 to 24 carbon atoms,

each of R R R is alkyl of from 1 to 24 atoms, and X is chlorine, the content of the softener in each liter of the composition amounting to at least about 20 grams; and

(c) an oxacyanine optical brightener having the formula C CH=O A 01130 -o-oH, N+ N 5H3 5H3 wherein A represents lower alkyl-phenyl-sulfonate.

References Cited UNITED STATES PATENTS 2,620,282 12/1952 Fry et al 117--33.5 2,649,385 8/1953 Kendall et al 117-33.5 2,940,816 6/1960 Sniegowski 2528.8 X 2,995,520 8/1961 Luvisi 2528.8 3,095,373 6/1963 Blomfield 2528.8 3,122,502 2/1964 Waldrnan 2528.8 3,256,180 6/1966 Weiss et al. 2528.8

HERBERT B. GUYNN, Primary Examiner U.S. Cl. X.R. 117-335, 139.5; 2528.8