US3575866A - New brighteners,compositions thereof and processes for using same - Google Patents

New brighteners,compositions thereof and processes for using same Download PDF

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US3575866A
US3575866A US878265A US3575866DA US3575866A US 3575866 A US3575866 A US 3575866A US 878265 A US878265 A US 878265A US 3575866D A US3575866D A US 3575866DA US 3575866 A US3575866 A US 3575866A
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brightener
example
composition
detergent
brightening
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Albert F Strobel
Sigmund C Catino
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GAF Chemicals Corp
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D249/00Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/22Naphthotriazoles
    • C07D249/24Naphthotriazoles with stilbene radicals attached in position 2
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60Optical bleaching or brightening
    • D06L4/65Optical bleaching or brightening with mixtures of optical brighteners

Abstract

A BRIGHTENER COMPOSITION PARTICULARLY ADAPTED FOR THE BRIGHTENING OF POLYESTERS COMPRISING (A) A COMPOUND OF THE FORMULA:

2-((PHENYL)-CH=CH-(1,4-PHENYLENE)-)-

2H-ANTHRO(2,3-D)TRIAZOLE

AND (B) A NON-IONIC SURFACTANT. WHEN SUCH A COMPOSITION IS EMPLOYED FOR BRIGHTENING OF A POLYESTER-COTTON BLEND, SUCH COMPOSITION MAY ADDITIONALLY CONTAIN A STILBENECYANURIC BRIGHTENER. THE ACTIVE BRIGHTENER IS PRECIPITATED BY DROWNING THE ABOVE COMPOSITION, EITHER ALONE OR TOGETHER WITH A SUITABLE DETERGENT IN THE WASH WATER.

Description

United States Patent U.S. Cl. 252-452 14 Claims ABSTRACT OF THE DISCLOSURE A brightener composition particularly adapted for the brightening of polyesters comprising (a) a compound of the formula:

and (b) a non-ionic surfactant. When such a composition is employed for brightening of a polyester-cotton blend, such composition may additionally contain a stilbenecyanuric brightener. The active brightener is precipitated by drowning the above composition, either alone or together with a suitable detergent in the wash water.

This application is a continuation-in-part of U.S. application Ser. No. 539,283, filed Apr. 1, 1966, now abandoned.

The present invention is directed to certain novel brightening compositions containing a stilbene naphthotrazole brightener, particularly effective in the brightening of polyester materials; more particularly, the present invention is directed to such a novel brightening composition comprising a stilbene naphthotriazole brightener in a nonionic surfactant, such composition when drowned in water being eifective to brighten polyester textiles.

It is well known that textiles tend to develop a yellowish shade on aging which cannot be removed by ordinary methods of bleaching or Washing. The heretofore used methods of bluing white material with blue pigments or fugitive blue dyestuffs have become quite obsolete in modern laundry practice and have been largely superseded by methods employing fluorescent optical bleaching agents or brighteners as additives to the soap or detergent in the washing bath. These brightening agents are usually conveniently supplied commercially in the form of intimate admixtures with the soap or detergent in bars, flakes, powders, etc. The fluorescent optical bleaching agents perform their desired function by virtue of their characteristic absorption of ultra-radiation and subsequent conversion of this energy to light energy within the visible spectrum. This converted and emitted light energy tends to neutralize any yellowness of the material and thereby increase the apparent whiteness thereof.

Compounds which have been suggested and employed as fluorescent brightening agents include the following:

(I) Acylated derivatives of 4,4-diamino-stilbene-2,2-

disulfonic acid.

(II) Acylated derivatives of 4,4-diamino-diphenyl-2,2-

disulfonic acid.

(III) Triazyl derivatives of diamino stilbene disulfonic acid.

ice

(IV) Triazyl derivatives of diamino diphenyl disulfonic acid.

(V) Acylated derivatives of diamino dibenzothiopheue dioxide, etc.

(VI) Stil'bene-cyanuric compounds.

Compounds of the Types I and II are disclosed in U.S. Pats. 2,518,059 and 2,643,198, and in British Pat. 584,484.

Compounds of the Types III and IV are disclosed in U.S. Pat. 2,618,636 and in application Ser. No. 381,856 published May 11, 1954 by the A.P.C.

Compounds of Type V are exemplified in U.S. Pats. 2,563,493 and 2,563,795.

Compounds of Type VI are exemplified in U.S. Pats. 2,526,668, 2,539,766, 2,694,064, 2,875,106, 2,473,475, 2,595,030, 2,612,501, 2,618,636, 2,658,064, 2,658,065, 2,660,578, 2,666,052, 2,667,458, 2,703,801, 2,742,43 4, 2,745,830, 2,840,557, 3,018,287, 3,127,270, 3,132,106, and 3,177,207.

In addition to the five types mentioned above, other triazyl compounds have been suggested. Thus, U.S. Pat. 2,713,054 discloses monotriazoles of the type:

l CH3 U.S. Pat. 2,713,055 discloses monotriazoles of the type:

NaOaS SOaNa U.S. Pat. 2,713,056 discloses monotriazoles of the type:

wherein X designates oxygen, sulfur, or imino, and Y alkyl or aryl.

U.S. Pat. 2,713,057 discloses monotriazoles containing a stilbene moiety of the type formulated in claim 2:

None of the aforementioned patents relates to stilbene monotriazoles containing a naphtho substituent. Such compounds, however, are disclosed in Pat. 2,784,183, and

representative of the compounds in the latter patent is the following compound:

N l N S 0311 Again, US. Pat. 2,784,184 relates to stilbene naphtho rnonotriazoles and bis-triazoles which, however, are devoid of water solubilizing groups and contain vicinal to the ethylene bridge of the stilbene moiety or para thereto at least one sulfonyl or substituted sulfonyl radical of It has now been discovered that a specific stilbene naphthomonotriazole is an outstanding brightening agent for hydrophobic fibers, i.e., so-called fine fabrics," and particularly for Dacron (polyester) and nylon, especially where these fibers are laundered in conjunction with cellulosic materials, e.g., cotton.

Thus, it has been discovered in accordance with the present invention that a compound of the formula:

is particularly effective as a brightener for hydrophobic fibers, particularly, polyesters and polyamides. In this regard, it has been discovered in accordance with the present invention that when such a brightener is dissolved in a non-ionic surfactant and drowned in water the active brightener precipitates in an active form particularly effective for the brightening of such fine fabrics.

Moreover, it has been found in accordance with the present invention that a particularly effective composition for the brightening of mixed hydrophobic fibers and cotton can be provided through the employment of a composition containing the aforementioned brightener dissolved in a non-ionic surfactant, such composition also containing a stilbene-cyanuric brightener of Type VI set forth above.

It is therefore a principal object of the present invention to provide novel fine fabric brightener compositions, particularly adapted for the brightening of polyester and polyamide materials alone or in combination with cotton.

It is yet a further object of the present invention to provide such novel brightener compositions comprising 2-(4-styrylphenyl)-2H-naphthotriazole dissolved in a nonionic surfactant, the active brightener being precipitated when such composition is drowned in water.

It is yet a further object of the present invention to provide such a novel brightener composition wherein such composition additionally contains a stilbene-cyanuric brightener capable of brightening the cotton portion of a mixed cotton-hydrophobic fiber blend.

Still further objects and advantages of the novel compositions of the present invention will become more apparent from the following more detailed description thereof.

The above objects and advantages of the present invention are achieved through a brightening composition comprising a specifically identified 2-(4-styrylphenyl)-2H- naphthotriazole brightener dissolved in a non-ionic sur- 1 factant. In accordance with the present invention, when such a brightener composition is drowned in water the active brightener is precipitated, such brightener being eminently suitable for the brightening of hydrophobic fibers, particularly polyesters. In this regard, as will be illustrated hereinafter, it is an essential feature of the present invention that the brightener be dissolved in a non-ionic surfactant since it is only through such combination of components that the outstanding brightening characteristics of the present invention can be achieved.

In addition, since hydrophobic fibers, particularly polyesters are conventionally blended with cotton fibers, an additional embodiment of the present invention includes within the above-noted composition a cyanuric cotton brightener. In this way, when such a composition is drowned in Water, the precipitated active brighteners can suitably brighten both the hydrophobic portion, i.e., polyester, and cotton portion of a suitable blended fabric.

As a still further embodiment of the present invention, such a brightener composition comprising the 2-(4-styrylphenyl)-2H-naphthotriazole dissolved in a non-ionic surfactant with or without an additional cyanuric brightener can be included within a conventional detergent composition. In this regard, such detergent can comprise any of the suitable anionic, cationic, non-ionic or amphoteric detergents conventionally employed in the laundering art. It is only essential in accordance with the present invention, however, that a non-ionic surfactant be present so as to dissolve the 2-(4-styrylphenyl)-2H-naphthotriazole brightener so as to allow precipitation when the composition is subsequently drowned in water during the washing and brightening operation.

Thus, it has now been discovered in accordance with the present invention that a brightener of the formula:

has the outstanding ability when combined with a nonionic surfactant to provide exceptional brightening results particularly when employed to brighten a hydrophobic fabric, particularly, polyesters and polyamides, i.e., Dacron and nylon, and polyester fabrics in particular. In this regard, as set forth above, such brightener has, unlike most optical brightening agents which preferentially brighten cotton or other cellulosic fibers when the same are present, the unique characteristic of preferentially brightening hydrophobic fibers such as Dacron and nylon, and thus being able to advantageously brighten Dacron, nylon and similar hydrophobic fibers even when mixed with cotton or other cellulosic fibers, either in a blended fabric or in a mixed laundry load of cotton fabrics and fine fabrics. Thus, with the novel compositions of the present invention which contain in addition to the abovenoted brightener and non-ionic surfactant a stilbenecyanuric type brightener of Type VI set forth above, instead of the two brighteners acting to adversely effect each others performance, there is instead some unique synergistic action between the two resulting in the brightening of not only cellulosic fibers, but also any Dacron and1 nylon fibers to which they may be applied simultan ous y.

The combination of the brightener of this invention with a cellulosic brightener and particularly one of the sulfonated stilbene-cyanuric Type V1 is unique in that brightening of both Dacron and nylon along with brightening of cellulose is achieved notwithstanding the fact that the brightener of this invention tends to cause the development of a yellowish cast on cellulose in the absence of the cellulose brightener, particularly in concentrations which are conventional for cellulosic brighteners (i.e., 0.1 to 0.4% by weight based on the weight of the detergent used).

The hydrophobic fiber brightener of the present invention is prepared by diazotizing 4-amino stilbene and coupling it to 2-naphthylarnine and thereafter oxidizing the resultant product to produce the desired triazole.

The 4-amino stilbene is a known compound (see B55: 1239) and has a melting point of 151 C. The compound is prepared from 4-nitro stilbene which is also a known compound with a reported melting point of 157 C. (B55: 1239). Specific details as to the preparation of compound A illustrating a preferred embodiment of the preparation thereof are given below.

While the brightener of the present invention may be employed in a variety of ways to effect brightening of fine fabrics, e.g., polyesters in particular, particularly advantageous results are achieved when the brightener is dissolved in a non-ionic surfactant and thereafter drowned in water during a conventional washing operation. Preferably, the brightener of the present invention is dissolved in from about 5 to 500 times its weight of a non-ionic surfactant having the molecular configuration of a condensation product of a reactive-hydrogen hydrophobe with from about 5 to about 30 moles of an alkylene oxide, preferably ethylene oxide, although propylene oxide, a butylene oxide, or mixtures thereof with ethylene oxide may be used. Such reactive-hydrogen hydrophobic compounds are well known in the detergent art and comprise alcohols, phenols, and less importantly, amides, sulfonamides, amines, and carboxylic acids all having at least 5 carbon atoms in the hydrophobe moiety and preferably, from to 35 carbon atoms therein.

Such non-ionic surface active agents are well known in the art and may be represented by the following general formula:

OHR-CHR R wherein R represents the residue of a hydrophobic organic compound containing a reactive hydrogen and R represents hydrogen, methyl or ethyl, with the proviso that the total number of carbon atoms in the R groups should not be higher than 2, and x represents an integer of from 3 to 150, usually from 6 to 50. Numerous specific non-ionic surfactants of this type, which may be used in the compositions of the present invention, are known in the art and include the polyalkylene oxide condensates of aliphatic and aromatic organic hydroxy compounds, carboxy compounds and amino compounds described in US. Pat. 1,970,578, of alkyl phenols described in US. Pat. 2,213,477, of carboxylic acid amines described in US. Pat. 2,085,706, and of sulfonamides described in US. Pat. 2,002,613, the disclosure of which are incorporated herein by reference. Typical examples of the alkylated phenols are:

isobutyl phenol n-butyl phenol diisobutyl phenol isoamyl phenol n-hexyl phenol isooctyl phenol n-octyl phenol di-n-octyl phenol di-isopropyl phenol nonyl phenol dinonyl phenol decyl phenol dodecyl phenol di-dodecyl phenol hexadecyl phenol tri-octyl phenol tri-nonyl phenol In the above described amides, sulfonamides, mercapto compounds and amines, R can be similar to R for alcohols and additionally, R may be an aryl moiety containing preferably at least about 8 carbon atoms, and most preferably, at least about 10 carbon atoms, and illustrative of these moieties mention may be made of alkylated phenyl such as isobutyl phenyl, diisobutyl phenyl, nonyl phenyl, dinonyl phenyl and the like.

Again, in accordance with the present invention, the novel brightener is dissolved in the non-ionic surface active compound in an amount such that the surface active compound is present in an amount of about 5 to 500 times the weight of the brightener. Preferably, an amount of surface active compound of from about 10 to about 300 times the weight of the brightener is advantageously utilized in accordance with the novel brightener compositions of the present invention.

As indicated above, when brightening a mixed hydrophobic fiber-cellulosic blend it is often desirable to include within the brightener composition a cyanuric brightener of Type VI previously set forth. The cyanuric brighteners Type VI which are eminently suited for use in accordance with the present invention for the brightening of mixed fibers may be represented by the following general formula (in the free acid form) wherein Y is sulfo or carboxy; wherein X and X are independently (1) hydrogen, (2) halogen, (3) alkyl, (4) hydroxy, (S) hydroxyalkyl, (6) primary alkylamino, (7) secondary alkylamino, (8) hydroxyalkylamino, (9) arylamino, (10) oxyphenyl, (11) oxyalkyl, (12) morpholino and the mono and di-sulfo derivatives of (6), (7), (9), (10), (11) and (12). It is preferred that at least one of X and X is other than hydrogen, halogen, and hydroxy and Y be sulfo.

Specific cyanuric brighteners as illustrative of the above include:

Generally, the cotton brightener is employed in a Weight ratio to the hydrophobic texile brightener of from 1:1 to 100:1, preferably in a weight ratio of :1 to 30: 1.

As previously indicated, it is often suitable to incorporate the brightener composition of brightener and nonionic surfactant in a suitable detergent composition so as to provide combined detergency and brightening characteristics. Thus, the non-ionic surfactant solution of brightener may be blended with a detergent formulation in any one of several ways.

Where the detergent in the laundering formulation is non-ionic, a solution of the brightener in the said nonionic is prepared within the concentration limits of about 0.2 to and preferably at a concentration of from 0.5 to 1%. This solution is then blended with an aliquot portion of the laundry detergent formulation (i.e., nonionic surfactant, builders, and other additives such as silicates, carboxymethylcellulose, etc.) to produce a paste. The paste is then further blended with the remaining portion of detergent formulation to give the desired brightener concentration therein which may vary from about 0.005% to about 0.5% by weight based on the total composition.

Where the detergent in the laundering formulation is anionic, a solution of the brightener in the non-ionic surface active agent is prepared but in more concentrated form (it is preferred to make a 5 %-10% solution) and add same to the anionic material. The preferred stage of addition is where the anionic is in the form of a 50-80% aqueous gel and preferably at an elevated temperature, e.g., C. The brightener solution is blended with the anionic solution in this form and this blend is added to the remaining solids, i.e., builders, fillers, etc. of the final formulation, after which spray drying results in the production of the brightened built anionic detergent composition.

In such detergent compositions which are to be used for all purpose laundry-brightening properties (i.e., including cellulosic textiles) the concentration of the cellulosic brightener may vary from about 0.05% to about 0.5% by weight based on the weight of the detergent. As with respect to the previous defined range limitations, however, it should be apparent that slightly lesser or greater amounts of the cellulosic brightener can be employed where desired for particular purposes.

The detergents which are suitable include the general classes of anionic and non-ionic types, and as usually formulated, they contain a major amount of inorganic builder salts (including alkaline salts) as fillers and detergency improvers. The most common alkaline builders are the phosphates, carbonates, borates and silicates. Typical phosphates include sodium tripolyphosphate, tetra potassium pyrophosphate, tetrasodium pyrophosphate, potassium tripolyphosphate and the like. Other additives which are conventionally used include anti-redeposition agents, soil suspending agents, and the like,

A typical detergent formulation may be represented by the following:

Ingredient: Parts by weight Detergent 15-40 Sodium tripolyphosphate 20-50 Sodium carbonate 20-50 Sodium sulfate 10-50 Sodium carboxy methyl cellulose 0.5-2 Sodium metasilicate 5-15 The detergent may be any of the non-ionic compounds described above and as examples of anionics, mention may be made of the following which have the indicated general structures in the free acid form:

(1) Alcohol sulfates (RCH OSO H wherein R is an aliphatic chain, preferably alkyl of 12 to 22 carbons) e.g., sodium lauryl sulfate.

(2) Alkyl aryl sulfonates A1S 03B wherein Ar is benzene or naphthalene and the Rs represent hydrogen or alkyl with about at least 6 carbons as alkyl substituents) e.g., sodium dodecyl benzene sulfonate.

(3) Alkyl sulfonates [RCH SO H wherein R is as in (1)] e.g., sodium lauryl sulfonate.

(4) Sulfonated amides l-r (BOON-CH2CH2S 03H wherein R is as in (1) and R is lower alkyl such as methyl, ethyl or cycloalkyl such as cyclopentyl or cyclohexyl) e.g., sodium-N-methyl-N-lauroyl taurate.

Sulfonated esters (RCOOCH CH SO H wherein R is as in (1)) e.g., oleic acid ester of sodium isethionate (6) Sulfonated amines (RNHSO H wherein R is as in (7) Anionic analogs of polyoxyalkylated phenols (RQMROM-ilho s 03H wherein R represents an alkyl or plurality of alkyl substituents, R is alkylene of 2 to 4 carbons and n is the number of moles of alkylene oxide (or equivalent) reacted and condensed with the phenolic hydroxy) e.g.

sodium salt of sulfated isooctylphenoxy nonaethyleneoxy ethanol.

Further examples and more details as to operable detergent compositions including the types of non-ionic surface active materials, anionic surface active materials and various additives including the inorganic builders may be found in the following US. patents:

(A) 2,941,951 which discloses numerous (1) non-ionic and anionic surfactants, (2) detersive and foam improvers such as the alkali metal phosphates, borates, carbonates, sulfates, chlorides, silicates, higher aliphatic alcohols, higher fatty acid amides and alkylolamides, e.g., lauroyl amide, lauroyl monoand di-alkylamides, lauroyl ethanolamide, and lauroyl diethanolamide,

(B) 2,965,678polyoxyethylene ethers of branched chain alcohols,

(B) 3,033,889phosphate ester of branched chain alcohols,

(D) 3,122,508phosphate ester surfactants and nonionic precursors thereof and numerous conventional additives,

(E) 3,168,478anionic phosphate surfactants, additives for detergent compositions including soil suspending agents, perfumes, deodorants, disinfectants, corrosion inhibitors, sequestrants, foam stabilizers, hydratropes, etc. and non-ionic precursors for the anionic compounds. The preferred non-ionic surfactants are the alkyl phenolethylene oxide condensates (see US. Pat. 2,941,951, column 4, lines 6-47).

The disclosures of the aforementioned US. patents are hereby incorporated by reference thereto as illustrating detergent compositions which are operable in the present invention.

As indicated above, the objects and advantages of the present invention are achieved through a novel brightener composition which comprises 2 (4 styrylphenyl) 2H- naphthotriazole dissolved in a non-ionic surfactant. In addition, in accordance with further embodiments of the present invention the novel brightener composition of the present invention can contain a suitable cotton brightener, particularly of the stilbene-cyanuric type, and such brightener composition with or without the cotton brightener may be included within a built detergent composition. In such composition, the detergent is preferably of the non-ionic or anionic type.

While the use of the novel brightener composition of the present invention has been emphasized in combination with detergent compositions for laundering fine fabrics, it is, of course, clear that the brightener may be used in other conventional ways to effect a brightening of the general class of hydrophobic synthetic polymers of the polyester, polyarnide, polyurethane, polyolefin, vinyl polymer types. Such techniques include particularly the melt incorporation of the brightener into the polymer prior to final shaping (i.e., molding, extruding, fiber forming, film forming, etc.).

The novel composition of the present invention and the advantages associated therewith will now be illustrated by reference to the following specific examples.

EXAMPLE 1 Preparation of hydrophobic textile brightener A:

At 40 C. a solution is prepared of 141.3 g. of 4-aminostilbene (0.725 mol: molecular weight 195) in 665 cc. of glacial acetic acid. This solution is then added gradually with stirring to a mixture of:

2000 cc. water 185 cc. hydrochloric acid (38% CF.)

The mixture is then stirred and cooled in an ice bath at 2 C. and while maintaining the temperature at from 2 to 5 C., there is added gradually 136.5 cc. of a sodium nitrite solution which contains 0.76 mol of sodium nitrite on a 100% basis. The resultant diazonium reaction product is then stirred for /2 hour at 05 C. in the presence of the slight excess of nitrite present therein. Thisexcess nitrite is then destroyed by adding just in excess of the stoichiometric amount of sulfamic acid required for this purpose.

There is then separately prepared a coupler solution by dissolving 115 g. of 2-naphthylamine (0.796 mol) in 333 cc. of glacial acetic acid. This coupler solution is then slowly added to the diazonium reaction product described above. The mixture is then set for 2 hours at 0-5 0, after which 200 g. of sodium acetate crystals are gradually sprinkled into the mixture. Stirring of the mixture is then continued for about 12 hours at 0-5 C. until there is obtained a negative test for diazo presence (spot coupling with H acid on paper). The resultant reaction mixture contains the final reaction product as a slurry in the aqueous medium and this slurry is filtered and the filter cake is then washed with 4000 cc. of Water. The resultant dye cake is then dried in air at C. The yield of product is 272 g. (107% of theoretical yield).

The dye produced above is then oxidized to the final brightener by the following procedure. Into a 3-liter 3-necked flask equipped with a stirrer, thermometer, reflux condenser and heating mantle there are charged:

136 g. of the dye produced above (0.35 mol) 1630 cc. picoline This mixture is stirred for a half hour at room temperature at 27 C. while there are added:

226.5 g. of copper sulfate penta hydrate.

This amount of the copper sulfate corresponds to 0.907 mol of copper. The mixture is then heated for 2 hours at 100 C. and permitted to cool down to 80-85 C. at which temperature there is added gradually to the mixture 131 g. of sodium sulfide (100% basis) to give a slight excess of sulfide (indicated by spot testing on paper with lead acetate solution). The charge is then further heated at 100 C. and clarified by filtering through a Celite filter. The filter cake which is copper sulfide is washed with 400 cc. with picoline (at C.). The mother liquor and wash liquor are then combined and cooled to 10 C. This cooling results in the formation of a copious precipitate which is filtered and the solid cake on the filter is washed with 200 cc. of methanol, then with 2000 cc. of water and finally air dried at 80 C. The resultant yield is 99.7 g. which is 82% of theory.

As pointed out above, the 4-amino stilbene starting material is a known compound but a particularly outstanding procedure for producing this compound is as follows:

Into a 1-liter 3-necked round bottom flask equipped with stirrer, thermometer, reflux condenser, and. thermostatically controlled water bath there are charged the following:

137 g. 4-nitrot0luene (molecular Weight 137) 127.2 g. benzaldehyde (1.2 mols) 150 cc. Carbowax 400 (polyethylene glycol, molecular weight about 400) 20 g. sodium N-methyl-p-toluene sulfonamide (0.097

mol) and 28 g. potassium carbonate, anhydrous (0.2 mol).

Percent by Weight Sodium dodecyl benzene sulfonate 15 Sodium tripolyphosphate 2O Tetrasodium pyrophosphate Sodium sulfate Sodium carbonate 3 Sodium carboxyrnethyl cellulose 1 Sodium metasilicate 5 2.4 ml. of the brightener solution which is prepared above The reaction mixture is stirred for hours at 60 C. 10 and which cfmtzllins g' z fif 5 t after which time there is mixed with the charge 2000 cc. S t 1S a so a mm ypoc cute 0 glve of Water at The Water layer is separated by .02 of available chlorine 1n the bath. A 4.5 g. swatch decantation and the residue is re-slurried in 2000 cc. of 9 cfitton andba g a Swatch of Dacmn are lmn3ersed 50 C. water. After settling, the water layer is again 15 m t i at an agitate: therem for 9 minutes decanted and the residue mixed with 1000 cc. of methanol 12 They are 4 tar y mused and and the mixture is then heated to C. After reaching dned' The Dacmn has a brightness readmg of this temperature, the methanolic solution is cooled down EXAMPLE 3 to 0 C. and the resultant precipitate is filtered and x washed with 200 cc. of methanol. The solid is then 20 Examp 1e 2 1s iepeated usmg mpkice bnghtelier d d t C Th ildi C nd A, an equal welght of a commercial brlghtener Wl'llCl'l i i Oven T 3, C a is a,{3-[N-methyl benzoxazolyl-(Z)]-ethylene. The bright Pro as a me Hg Pom o ness of the Dacron in this procedure is only 12.

EXAMPLE 2 The outstanding bringtening effect of the brightener 25 MPLE 4 of this invention is illustrated on a Dacron textile ma- E ample 2 is again repeated using in place of brightterial as follows. 0.1 g. of the brightener produced in ener A, an equal weight of the commercial styryl naphtho- EXample 1 is dlssolved n 0 cc. Of nonyl phenoxy nona oxazole brightener. The brightness of the Dacron here ethyleneoxy ethanol (a liquid non-ionic surface active i 24, agent produced by the condensation on nonyl phenol 30 EXAMPLE 5 with 10 mols of ethylene oxide). The resultant solution is then diluted to 1 liter with water. To cc. of water Example 2 is still once more repeated using in place there are added 0.4 g. of a commercial detergent formuof brightener A, an equal weight of the following brightlation which comprises as the main ingredient: eners:

Compound Brightness (1)-.- N\ 20 N- -CH=OH 502011 U N Q Q l N 01 EXAMPLE 6 Example 2 is again repeated except that the hypochlorite is eliminated. Similar excellent results are obtained.

EXAMPLE 7 Examples 3 and 4 are repeated eliminating the hypochlorite. No improvement in brightness is noted.

EXAMPLE 8 Example 2 is again repeated except that 0.008 g. of brightener A is prepared in a solution of 100 ml. of dimethyl formamide and a 2 ml. aliquot of this solution is added to the hypochlorite-detergent bath. The brightness of the Dacron so treated is 19.

EXAMPLE 9 Examples 3 and 4 are repeated following the modifications of Example 8, and the resultant Dacron swatches have brightness values of 7 and 9, respectively.

EXAMPLE 10 Employing compound 3 of Example in the procedure of Example 8, there results a brightness reading on the Dacron of 11.

Examples 8 through demonstrate that even at the minuscule amounts used in these examples, there is a significant difference in brightening among the brighteners used and brightener A is again far superior.

EXAMPLE 11 Example 8 is again repeated except that in place of dimethyl formarnide, the brightener is prepared in solution in hot methyl Cellosolve (ethylene glycol monomethyl ether). The results are substantially the same as those obtained in Example 8.

EXAMPLE 12 Example 8 is again repeated except that 300 ml. of hot ethanol is used as the solvent in place of the dimethyl formamide and 6 ml. aliquot of this solution is added to the laundering bath. Similar results are obtained as in Example 8.

As pointed out above, mixed fiber batches are preferably brightened with a combination brightener, i.e., cellulosic brightener plus brightener A, and this is demonstrated in the following examples.

EXAMPLE 13 The procedure of Example 8 is repeated except that the amount of brightener A used is 0.00008 g. (0.02% by weight based on the weight of the detergent), and there is additionally added to the bath 0.0008 g. (0.2% by weight based on the weight of the detergent) of a cellulosic brightener of structure X above. The Dacron swatch is found to have a brightness of 9 and the cellulose sw atch a brightness of about 100.

EXAMPLE 14 Example 13 is repeated except that brightener A is replaced by an equal weight of the brightener of Example 3. The Dacron swatch treated in this manner has a brightness of 4, and the cellulose a brightness of about 100. The above two examples demonstrate the excellent brightening of the cellulose by the cellulosic brightener as well as the far superior brightening of the Dacron where brightener A is included in the bath vis-a-vis the Dacron brightening achieved with the commercial brightener.

EXAMPLE 15 Example 13 is repeated replacing brightener A by an equal weight of brightener compound (1) of Example 5. The brightness of the Dacron is improved slightly over that produced in Example 14 but the product is still much inferior to the brightened Dacron of Example 13. .As in Examples 13 and 14, the cellulosic material has a bri htness value of about 100.

EXAMPLE 16 Example 13 is once more repeated except that the detergent used contains in place of the :anionic surfactant component, sodium dodecyl benzene sulfonate, an equal weight of nonyl phenoxy nonaethyleneoxy ethanol. The brightness reading on the Dacron so treated is 10. Replacing brightener A with the commercial brightener of Example 3 produces a brightness on the Dacron of 5.

EXAMPLE 17 The procedure of Example 13 is again repeated except that brightener A is employed at a concentration of 0.05%. The Dacron swatch treated in this manner is found to have a brightness of 17 and the cellulose swatch a brightness, again, of about 100. At this concentration, replacing brightener A with an equal weight of the bright ener of Example 3, there results a brightening of a Dacron swatch to the extent of a brightness value of about 8.

EXAMPLE 18 The general procedure of Example 13 is again once more repeated but the bath employed is one of 200 ml. in volume (i.e., a liquor to total cloth ratio of 40:1 instead of 20:1 as in Example '13). The Dacron swatch which results from this treatment has a brightness value of 8.

EXAMPLE 19 Example 2 is repeated except that in the detergent formula the sodium dodecyl benzene sulfonate is replaced by sodium decyl benzene sulfonate. Comparable results are obtained.

EXAMPLE 20 Example 2 is once more repeated in each of the following examples except that in each instance a different anionic detergent is employed in the indicated amounts in place of the sodium dodecyl benzene sulfonate of Example 2:

(A) 15% of cyclohexyl ammonium dodecyl benzene sulfonate (B) 10% ammonium diisobutyl benzene sulfonate (C) 12% sodium octadecyl benzene sulfonate (D) 15% sodium diisobutyl naphthalene sulfonate (E) 15% sodium keryl benzene sulfonate Substantially the same results are obtained as in Example 2. In the above examples A through E the difierence between the amount used and 15% is made up by adding that difference as a percent increase in the amount of sodium sulfonate in the detergent formulation.

EXAMPLE 21 Example 2 is again repeated except that the detergent employed comprises the following ingredients in the ratio of the indicated parts:

Parts Surfactant (anionic phosphate ester described in Example 74 of US. Pat. 3,122,508) 10 Tetrapotassium pyrophosphate 25 Sodium oleate 7.2 Sodium metasilicate 3 Sodium xylene sulfonate 5 Carboxy methyl cellulose 0.5 Potassium hydroxide 2.5

Excellent brightness of the Dacron is obtained.

In the foregoing examples the brighteners are added to the detergent bath as a separate ingredient apart from the surfactant composition. In the following examples the brighteners employed are incorporated first into the detergent formulation and then the latter is added to the 100 ml. of Water to conduct the tests in the brightening of the various swatches immersed therein.

EXAMPLE 22 One part of brightener A is added to ten parts of the liquid non-ionic surface active material described in Example 2. The mixture is heated to 130 C. whereby this solution of the brightener is obtained. At this temperature the solution is then added to a hot (100 C.) slurry of an aqueous sodium dodecyl benzene sulfonate slurry containing about 75% active sulfonate and the balance water. This mixture is then thoroughly stirred to obtain uniform distribution of the brightener solution in the sulfonate slurry and the entire mixture is thereafter dried on a hot rotating drum. The amount of brightener solution used is adjusted so that in the finalproduct there is present 0.4% by weight of brightener. This brightener sulfonate combination is then employed in place of the 15% by weight of sodium dodecyl benzene sulfonate used in Example 2 and in combination with the remaining additives set out as being present in the commercial detergent formulation recited in Example 2. In the final detergent formulation there is present about 0.06% by weight of brightener A based on the weight of the total ingredients of the detergent composition. The general procedure of Example 2 is then carried out to effect the brightening of the Dacron as described in that example. The brightness reading of the final dry Dacron swatch is 38. Repeating this procedure except that the commercial brightener of Example 3 is used in place of brightener A results in the Dacron swatch having a brightness of only 9.

While brightener A of the present invention is most outstanding when employed in the manner described in the aforementioned examples, it may also be used, however, in combination with polymers and particularly polyesters of the Dacron type in a melt incorporation technique. In general, to incorporate brightener A in polyethylene terephthalate, the latter is melted under vacuum at 250 C. with about 0.01% of brightener A and the melt then fashioned into any conventional form desired, such as films, fibers, or molded into any suitable shape. The resultant products exhibit not only outstanding brightness but it is also found that the brightener is remarkably stable to ambient influences. As evidenced by the fact that after six months exposure outdoors, less than 15% of the fluorescence (brightness) is lost.

In Example 1 above there has been set forth a specific and detailed procedure for producing the brightener A of this invention. It has also been found that this compound may be produced by a somewhat modified process which is completely unforseen, particularly with regard to the outstanding yields which are obtained. By this modification it is possible to obtain the amino azo intermediate (the product used in the oxidation step to produce the final triazole) in most quantitative yields. This modification follows the general procedure of Example 1 except that in place of the 2-naphthylamine coupling component there is employed an equivalent weight (i.e. 0.796 mol) of l-sulfo-Z-naphthylamine and no glacial acetic acid is necessary since the coupler is soluble in water. After an aqueous solution of the coupler has been slowly added to the diazonium compound, the pH of the mixture is adjusted to about 7.5 with soda ash, the mixture then heated to 45 C. and thereafter stirred for four hours. The product is isolated as in Example 1 and oxidized to the triazole similar as in that example. Any unreacted azoamino compound may be destroyed by acidifying and warming the material prior to isolation and recovery in the manner described in Example 1. This modified form of the process for producing brightener A not only gives rise to exceptional yields of very pure product but furthermore avoids the use of 2-naphthylamine as a coupler,- Which may be objectionable.

EXAMPLE 23 Example 22 is repeated except that the 10 parts nonionic surface active material used to prepare the initial brightener solution is replaced by the following:

(A) 10 parts of octyl phenoxy dodeca ethylene oxy ethanol,

(B) 20 parts of nonyl phenoxy nona ethylene oxy ethanol,

(H) 10 parts of a tridecyl alcohol and 6 mols of ethylene oxide condensate,

(I) 20 parts of a dodecyl amine and 20 moles of ethylene oxide condensate,

(I) 15 parts of an isobutyl benzene sulfonamide and 30 mols of ethylene oxide condensate.

The results in each instance are comparable to Example 22.

EXAMPLE 24 (A]) Example 2 is repeated 10 times except that in each case the 20 cc. of nonyl phenoxy nona ethylene oxy ethanol of that example is replaced by an equal weight of the surface active non-ionic compounds in Example 23 (A-I).

EXAMPLE 25 The general technique of Example 22 is followed to prepare a brightener A-detergent formulation based on the detergent described in Example 16. A 10% solution of the brightener in the non-ionic surface active compound is first prepared and this is blended with a portion of the remaining ingredients to yield a paste containing about 1% brightener. This paste is then further blended with the remaining ingredients on a ribbon blender to yield the final composition containing about 0.04% brightener A. In this example the cellulosic brightener is omitted. If the latter is desired, it may be added separately and blended with the paste or in the final mixing step using any desirable concentration from about 0.05% to about 0.5%.

EXAMPLE 26 Example 13 is repeated several times replacing in each instance the cellulosic brightener X by the following:

(A) cellulosic brightener I, (B) cellulosic brightener III, (C) cellulosic brightener IV, (D) cellulosic brightener V, (E) cellulosic brightener VI, (F) cellulosic brightener VIII.

The results are comparable to Example 13.

EXAMPLE 27 Example 22 is repeated except that there is additionally added to the hot slurry of sodium dodecyl benzene sulfonate sufficient of cellulosic brightene'r X to give a final concentration in the detergent of 0.3%

@ Q-Qn dissolved in (b) a liquid non-ionic surfactant, the amount of (b) being to 500 times by weight the amount of (a) which is present in an amount of about 0.0050.5% based on the weight of the actual composition.

2. The brightener composition of claim 1 wherein said liquid non-ionic surfactant (b) is a condensation roduct of an alkyl phenol containing from about to 35 carbon atoms and from 5 to about moles of ethylene oxide per mole of said phenol.

3. The brightener composition of claim 1 wherein said liquid non-ionic surfactant (b) is a condensation product of an alcohol of about 6 to 30 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said alcohol.

4. The brightener composition of claim 1 wherein said composition additionally contains (0) a stilbene-cyanuric brightener in a ratio of (c) to (a) of from about 1:1 to about 100:1.

5. The brightener composition of claim 4 wherein the ratio of (c) to (a) is from 10:1 to 30: 1.

6. The brightener composition of claim 4 wherein said liquid non-ionic surfactant (b) is a condensation product of an alkyl phenol containing from about 10 to carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said phenol.

7. The brightener composition of claim 4 wherein said liquid non-ionic surfactant (b) is a condensation product of an alcohol of about 6 to 30 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said alcohol.

8. A detergent composition consisting essentially of (1) a nonionic or anionic detergent and (2) a brightener composition consisting essentially of (a) a compound of the formula dissolved in (b) a liquid non-ionic surfactant, the amount of (b) being 5 to 500 times by weight the amount of (a), said brightener composition being present in such an amount that said compound (a) is present in an amount of 0.005% to about 0.5% by weight based on the total composition.

9,. The detergent composition of claim 8 wherein said liquid non-ionic surfactant (b) is a condensation product of an alkyl phenol containing from about 10 to 35 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said phenol.

The detergent composition of claim 8 wherein said liquid non-ionic surfactant (b) is a condensation product of an alcohol of about 6 to 30 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said alcohol.

11. The detergent composition of claim 8 wherein said composition additionally contains in said brightener composition (c) a stilbene-cyanuric brightener in a ratio of (c) to (a) of from about 1:1 to about :1.

12. The detergent composition of claim 11 wherein the ratio of (c) to (a) is from 10:1 to about 30:1.

13. The detergent composition of claim 11 wherein said liquid non-ionic surfactant (b) is a condensation product of an alkyl phenol containing from about 10 to 35 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said phenol.

14. The detergent composition of claim 11 wherein said liquid non-ionic surfactant (b) is a condensation product of an alcohol of about 6 to 30 carbon atoms and from 5 to about 30 moles of ethylene oxide per mole of said alcohol.

References Cited UNITED STATES PATENTS 2,213,477 9/1940 Steindorfi" et al. 25289 2,703,801 3/1955 Rottschaefer et al. 260240B 2,713,046 7/1955 Williams et a1 260240B 2,793,192 5/1957 LeaW/itt 252-890B 2,840,557 6/1958 Williams et al 260240B 3,288,786 11/1966 Strobel et a1. 252301.2

FOREIGN PATENTS 12,834 3/1962 Japan.

LEON D. ROSDOL, Primary Examiner W. E. SCHULZ, Assistant Examiner US. Cl. X.R.

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954675A (en) * 1972-06-01 1976-05-04 Colgate-Palmolive Company Heavy duty oxidizing bleach stable liquid laundry detergent
FR2375303A1 (en) * 1976-12-21 1978-07-21 Hoechst Ag Preparation comprising poorly soluble or insoluble colorants of the constituents in water
US4298490A (en) * 1978-12-22 1981-11-03 Ciba-Geigy Corporation Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents
EP0321393A1 (en) * 1987-11-27 1989-06-21 Ciba-Geigy Ag Optical brightener dispersion
EP0323399A1 (en) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Optical brightener dispersion
US20060246383A1 (en) * 2005-04-29 2006-11-02 Kai-Kong Iu Amphoteric stilbene composition
US20090223003A1 (en) * 2004-09-23 2009-09-10 Stephen Norman Batchelor Laundry treatment compositions
US20100326319A1 (en) * 2009-06-25 2010-12-30 Hyundai Motor Company White rust inhibiting composition for aluminum parts

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954675A (en) * 1972-06-01 1976-05-04 Colgate-Palmolive Company Heavy duty oxidizing bleach stable liquid laundry detergent
FR2375303A1 (en) * 1976-12-21 1978-07-21 Hoechst Ag Preparation comprising poorly soluble or insoluble colorants of the constituents in water
US4298490A (en) * 1978-12-22 1981-11-03 Ciba-Geigy Corporation Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents
EP0321393A1 (en) * 1987-11-27 1989-06-21 Ciba-Geigy Ag Optical brightener dispersion
EP0323399A1 (en) * 1987-11-27 1989-07-05 Ciba-Geigy Ag Optical brightener dispersion
US5051111A (en) * 1987-11-27 1991-09-24 Ciba-Geigy Corporation Whitener dispersion
US20090223003A1 (en) * 2004-09-23 2009-09-10 Stephen Norman Batchelor Laundry treatment compositions
US8268016B2 (en) 2004-09-23 2012-09-18 The Sun Products Corporation Laundry treatment compositions
US8715369B2 (en) 2004-09-23 2014-05-06 The Sun Products Corporation Laundry treatment compositions
US7789917B2 (en) 2005-04-29 2010-09-07 Hewlett-Packard Development Company, L.P. Amphoteric stilbene composition
US20060246383A1 (en) * 2005-04-29 2006-11-02 Kai-Kong Iu Amphoteric stilbene composition
US20080290320A1 (en) * 2005-04-29 2008-11-27 Kai Kong Iu Amphoteric stilbene composition
US20100326319A1 (en) * 2009-06-25 2010-12-30 Hyundai Motor Company White rust inhibiting composition for aluminum parts
US7988775B2 (en) * 2009-06-25 2011-08-02 Hyundai Motor Company White rust inhibiting composition for aluminum parts

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