US2385765A - Textile finishing - Google Patents

Description

rn uaasesaza'lms UNITED i sfrA'rs I I 2.3mm

' mm rmrsnmo Jack :1. "Thurston, Cos cob, com, assignor to 3 a corporation of Maine ldclaims. -This invention relates to the treating and fin- Oyauamid Company, New York, N. Y.,

application August so, 1941, .v Serial No. 409,112

ishing of textiles and textile-forming materials such as cotton, linen, wool, viscose, silk. cellulose.

acetate, spun rayon and thelika- More particu- .lariy, the invention-relatesto textile finishing processes, to finishing compositions and to textiles finished with compositions consisting of'or containing higher aikyl guanamines and their al-. dehyde condensation products, as will be de-.

scribed.

A wide variety of softening agents, lubricants, creaseproofing agents and waterproofing agents have heretofore been applied to textile threads and fibers. The treatment of textiles for these and similar purposes such as shrinkproofing is known as textile finishing, and the agents employ'ed are known as textile finishing agents. I

- soluble in hot mineral spirits, in. glyceride oils and in .xylene,'but are. insoluble or sparingly sol uble in water. As a rule the compounds of my, invention show increasing solubility in the above solvents with increasing chain length and .with

is a principal object of the present invention to provide a new class of textile finishing agents having improved softening, waterproofing and other properties, and to provide new and im-. proved textile finishing processes employing such materials. A further important feature of the invention resides in the provision of cotton, linen, wool, silk, cellulose ester and other yarns, threads or fabrics finished with compositions containin higher alkyl guanamines and their reaction prodnets and having improved water-resistance and a more desirable hand.

' I have found that the higher allryl guanamines, in which the alkyl group attached to the 2-carbon atom of the triazine nucleus contains at least 7 carbon atoms with or without other substituents in addition to hydrogen, possess remarkable properties when applied to textiles of the above and similar classes. Many of these guanamines, as such, have softening and lubricating properties for certain textile fibers, notably cottop, and they also impart water-repellent properties to a marked degree. Moreover, these waterrepellent properties may be greatly enhanced by further reaction of the guanamines, either before crystalline solids havingrelatively high melting points and good stability against heat and discoloration. The unsubstituted members of the series have melting points in the range of about 7 '75-150 C. while the corresponding mono-N-acyl derivatives have much higher meltin points. On the other hand the melting points of the N-N'- diacyl compounds are considerably lower than the melting points of the corresponding unsubstituted guanamine and wide range of comor after their application to the fiber, or both,

pounds of varying physical characteristics is therefore presented by the invention in its broader aspects. Most of the higher alkyl guanamines are increased branching of the chain. I

l'he higher alkyl guanamines as a class are compounds corresponding to the formula m which R is a saturated or unsaturated al phatic or .cycloaliphatic group containing at least 7 carbon atoms attached to the triazine nucleus by.

a carbon-to-carbon bond. This group may be further substituted by halogen, hydroxy, alkoxy, oxyaryl, aryloxy, carboxylic, carbonyl, sulfonic, amino, amido or other groups as will be subsequently explained, and any one or more or A, B and X may be H or any other substituent such as acyl, alkyl, cycloalkyl, aromatic and the like.

A few representative compounds falling withinthe above definition, and which may be applied to textile threads or fibers'to vary the properties thereof in accordance with the present invention,

are as follows: J

(1) Representative long chain saturated or unsaturated aliphatic guanamines are octanoflilanamine, decanoguanamine, lauroguanamine, myristoguanamine, palmitroguanamine, stearogu'anamine, oieoguanamine, linoleoguanamine and similar higher alkyl guanamines obtained by the reaction of biguanide or substituted biguanides with vegetal (animal and vegetable) oils, the fatty acids thereof or preferably the methyl esters of these fatty acids such as those obtained from olive oil, hydrogenated cotton seed oil, coconut oil, teaseed oil, peanut oil and the like. Usually guanamines obtained from saturated higher fattyacids or from fatty acids having only a limited degree of unsaturation such as oleic acid are pre-- ferred in practicing the invention, as the more unsaturated compounds are less stable to oxidation and to chlorine from laundry bleachs.

(2) Representative branched chain guanamines,

which may be used in practicing the invention aremethyl-isoamylacetoguanamine, N-acyl acetoguanamines, beta beta di-n-propylpropionoguanamine, di-isobutylacetoguanamine, n-amyin-heptylacetoguanamine, di-n heptyiacetoguanamine, di-n-octylacetoguanainine, ethyl-n-buethyl -isoamylacetoguanav etoguanamine, 4' ethyl 2 octanoguanamine. Representative cycloaliphatic guanamine are those obtained. for example, by condensing naphthenic acids and their aliphatic esters with 'biguanide or substituted biguanides and similar condensation products of maleic acid or anhydride with tung oil and with terpenes, and ortho-\ carboxy-endomethylene tetrahydrobenzoguana- I rupted, for I have found that good results are obtainable with compounds of both types when the radical contains a total of at least seven carbon atoms. Thus, for example, beta-octadecylamino-propionioguanamine and stearylaminoacetoguanamine possess softening and waterproofing properties for textiles comparable to those of stearoguanamine, particularly when con- 1 densed with formaldehyde.

Other compounds illustrative of the class of guanamines containing organic substituents are the higher alkoxyalkyl guanamines such as beta octadecoxypropionoguanamine and beta amyloxypropionoguanamine. Compounds representative of other groups that may be. present are omega-carbomethoxygonoguanamines, omega-carboxypelargonoguanaf mine, beta-N dibutylcarbamyl propionoguanamine, alpha-methoxy-beta-N octylcarbamylpropionoguanamine (CaHrLNHCOCHzCI-I, (on3) camel) beta-carboxy beta amyloxypropionoguanamine and omega-acetyl undecanoguanamine.

tion in the presence of alkaline catalysts. Metal alcoholates are particularly useful for this purpose, and sodium methylate is the preferred catalyst. The condensation product is usually recovered by filtration and purified by recrystallization from methanol. other alcohols, acetone, methylethyl ketone, hot water or other suitable 1 solvents. Many of the N-substituted guanamines may also be prepared from the corresponding un- 'salts, preferably in the by fusion with amine presence of a fiux such substituted guanamines as phenol and 'a condensation catalyst such as pelargonoguanamine, omegacarbobutoxypelar- (4) As is pointed out in my copending appli cation Serial No. 409,113, filed concurrently herewith the presence of substituents on one or both of the amino groups of the guanamines is frequently of advantage in textile treatment, for these substituentsmay modify the solubilitiesof the compounds and their compatibility with resins, waxes, starches, gums and other ingredients of textile finishing compositions with which the guanamines may be employed. Representative N-substituted higher alkyl guanamines that have been prepared and tested are 4-N-phenyl-lauroguanamine, 4-N-butyl-2 (alpha ethyl) hexanoguanamine, 4-N-octanoyl-octanoguanamine, 4-N- lauroyl-lauroguanamine, 4- -stearoyl-stearoguanamine, 4-N-phenyl-stearoguanamine and disubstituted derivatives such as 4-N-phenyl-6-N- myristoyl-myristoguanamine and 4,6-N ,N'-diacetyl decanoguanamine. I

The above and other guanamines falling within the scope of the invention may be prepared by reacting with unsubstituted or substituted aliphaticand cycloaliphatic carboxylic acids and their esters and halides. When the acid' halides are used the reaction usually proceeds smoothly upon simple admixture of the reagents in .the presence of inert solvents, but when the esters are employed it is frequently desirable to carry out the reac- 'and a permanent laundry-resistant zinc chloride. -N-acyl guanamines may be prepared insimilar manner by heating the unsub-- tituted guanamine with an acid chloride or acid anhydride.

It is an important advantage of the higher alkyl guanamines falling within the scope of the present invention that they will combine with formaldehyde, acetaldehyde, butyraldehyde and other aldehydes to form condensation products, for it is in this form that they are most useful as finishing agents for textiles. When dispersible resins are desired it is usually advisable to employ guanamines containing at least two replaceable amino hydrogen atoms and to use rather mild conditions for thealdehyde condensation, such as by agitating the aldehyde and guanamine solution at 50-70" C. until the reaction is complete,-and an inert solvent may be used to maintain the guanamine in a dispersed form at these temperatures. The resulting resin solutions which are first formed can usually be diluted with limited quantities of water, but upon continued heating or upon reaction at higher temeratures a hydrophobic resin isproduced. Further polymerization is obtained upon heating the resin after its application to the textile fibers,

waterproofing effect is obtained when the fiber is first-impregnated with the resin in its water-dispersible stage and then subsequently heated to further cure the resin to the watereinsoluble stage.

Although other aldehydes may be employed I prefer to condense the guanamlnes with formaldehyde, which may be used in the form of ordinary 3'l% formalin solutions, or as strong aqueous formaldehyde solutions of 40-50% strength stabilized by the addition of 4-10% of melamine, or as paraformaldehyde. At least one mole of formaldehyde for each mole of guanamine should be used, and in the case of N-unsubstituted guanamines at least two moles of formaldehyde should be employed. When higher formaldehyde ratios of the order of 6-8 moles or more for each mole of the guanamine are employed the condensation product is more easily dispersibiguanide or substituted biguanides g ble in water.

The guanamine-formaldehyde condensation products are quite easy to obtain in the form of substantially monomolecular products; that is to say, as methylol guanamines. When lauroguanamine, stearoguanamlne and other N-unsubstituted long chain guanamines are combined with formaldehyde under the mild conditions described above there is first obtained a hydrophile syrup. Upon evaporation of the solvent or solvents under reduced pressure at 30-40 C. methylol guanamines are obtained which are soluble in hot'mineral spirits, hot alcohols and hot xylene and which can be crystallized from these solvents upon cooling, and which are compatible with urea-formaldehyde, melamine formaldehyde and alkyd resins. These compounds can be kylated by heating with primary alcohols such as methanol, ethanol and butanol in the presence of small amounts of phosphoric acid, oxalic acid or hydrochloric acid-with azetropic distillation of,

the water of condensation and the resultingzproducts may be applied to textiles from their solutions in organic solvents-as'creaseproofing agents and water-repellents.

Many of the higheralkyl guanaminesare soluble in such organic solvents as acetone, toluene, dioxane and ethers of ethylene glycol and may be applied as such to textiles as softening agents.

" applying-any ofthe compositions f;

The aldehyde condensation products can alsobe I able excessover. the amountfot. and the ,retention'of'the flnlsh., on"

laundering is thereby gr atiyjn iv As has been stated. above, one' ot ful methods of preparing textile nesting. containing higher alkyl, guanaminecompounds:

is. with the aid of dispersing agents; 7 Aqtypical procedure of this kind, which ior tion to textiles, is as follows:

A solution of the higher yr asanrien hyde resin is prepared in methanol; ethanol,

I propanol or other suitable isolventfby iiieating alcohols containing an ethylene oxide ring are also good dispersing agents.

Another class of agents that are particularly well suited for use as dispersing agents are aliphatic and cycloaliphatic substituted guanamines in which the alkyl radical contains a sulfonic group, such as omega-suli'odecanoguanamine or one or more carboxylic acid groups such' as omega-carboxy-propionoguanamine, omega-carboxy pelargonoguanamine and the like. These compounds in which the 2-aliphatic or cycloaliphatic substituent contains a hydrophilic group may be mixed with the guanamine resins to be solubilized in amounts of 5% to 15% or more, or they may be themselves reacted with the aidehyde either alone or in admixture with the other guanamines without losing their water dispersing properties. Another compound which aids in the water dispersal of the higher alkyl guanamine resins is the guanamine obtained by condensing biguanide with Petrex, which is a dlene condensation product of pinene with maleic anhydride.

Additional solubilizing and dispersing agents are also described and claimed in the copending application of Stiegler, Fluck and Thurston,

Serial No. 409,114, filed concurrently herewith. As is pointed out in that application, such wetting and emulsifying agents as sodisopropyl naphthalene sulfonate, sodium lauryl sulfate, glycerine and other polyhydric alcohols, partially or completely neutralized sulfite cellulose liquor, sodium,

' ammonium and ethanolamine stearate, oleate and with agitation. An aqueous Y dispersion'ofa 3 gum or other suitable binding agent is thenipre-i pared having a concentration suitable for'application to the fiberi for example, a solution of 10-15 parts or-more of water-soluble urea-formaldehyde resin or of methylated methylol melamine in sufilcient water to make parts. About 5-10 parts by weight ofa 5% solution of a suitable dispersing agent such as sodium isopropyl naphthalene sulfonate is added to this bath and the alkyl guanamine resin solution is poured in with stirring while maintaining the temperature at about F. A dispersion having an extremely fine particle size is thus obtained, to which a curing accelerator may be added to speed up the setting of the resin after its application to the fiber if'desired. Four per cent based on the total resin solids of a mixture of 4 parts hexamethylene tetramine and 30 parts of diammonium phosphate has been used to advantage. The cloth to be treated is immersed in this bath and then passed through squeezing rolls adjusted to a tension such that the quantity of treating solution retained on the cloth is approximately equal to the weight of the fabric. The treated cloth is then dried at about 250 F. and heated for a short time at higher temperatures to cure the resin. A permanent and laundry-resistant waterproof finish is thereby imparted to the cloth.

It should be understood that the above described aqueous dispersion of higher alkyl guanamines in admixture with urea-formaldehyde and particularly methylated melamine-formaldehyde The invention will be illustrated incl-cater detail by the following specific examples, which show representative compositions includedthere- 5 in. It should be understood, however, that although these examples may describe in detail some of the more specific details of the invention they are given primarily for illustrative purposes tion products to textiles as the principal finish ing agent these compounds may be applied in admixture with resins, gums, balsams and other binders that will give increased permanency to the finish. Thus, for example, urea-formaldehyde resins, melamine-formaldehyde resins, phenol-formaldehyde resins, alkyd resins or any other curing type of resin may be used to assist and the invention in its broader aspects is not limited thereto. I

- Example 1 Stearoguanamine was prepared by reacting parts by weight of biguanide and 300 parts of i was agitated until homogeneous and then allowed in binding the guanamine to the fiber; These additional binding agents can be used in considerto stand for about 65 hours, whereupon the pre methyl ethyl ketone and an almost colorless product melting at 112-114 C. was obtained. Further purification ,by recrystallization gave a] stearoguanamine melting at 1l6-117 C., but for min m-1. l

the product ofiower' melting point issatisf'actory. I I t I pecanoguanamine. n-octanoguanamine. '2'- ethylhexanoguanamine, laureand densation products I myristoguanamine were prepared by substan- I and formaldehyde conwere obtained by agitating with 37% aqueous formalin solutions at ls-80 c.

' in the ratio ofv 3-8 moles formaldehyde for each mole of the guanamine for periods of time ,varyt.25 hours 1:03 hours ing from abou depending tl'iesta'ge of polymerization procedure described in Example 2. After heat?- ing at 70 C. for 2.5 hours the thick resin was dried to give a solid which was soluble in arn monia. v

' "Impregnatingbathswere prepared by dissolvf ing the mixed resin'in ammonia in varying con- -centrations, and the finish was applied to cotton upon thepH of the solution, the guanamine used; I

product desired, and

whether the formalin was diluted with an orzanic solventv such as methanol or ethanol. In. the presence of alcohol as a diluent and at pH values from about 7.0 to

1-The preparation of 'a stearoguanamine-fonnaldehyde is typical; and is as follows:

mixture of 42 parts by weight of steamguana'mine prepared by the above described process and imparts of 37% aqueous formaldehyde washeated at 70 C. for about 12 minutes with vigorous stirring. As the stearoguanaminebecame warm it softened and emulsified, and after 12 minutes the formaldehyde condensation proddehydration. 4

not "was obtained. When the reaction mixture .was cooled with stirring the resin remainedin the form or a stiff emulsion which could be dispensed in water, but evaporation of the water at 35-40 9.0 the reaction times were much longer than in the absence of the diluent.

i t m 'ried out by agitating the samples in trichlorethyle Percale-and to spun-rayon dress goods. pregnated samples were F. and cured 3 minutes I addition of sewing accelerator to the bath. Boapings were-made using in: machine for 1 hour I h Drrcleaning tests were'can" ene for minutes.

7 '1% and 10% ofthe finish was applied cot-' The 1% sample, before seeping,-

ton percale. possessed a soft hand and a tendency-to repel water; the hand of the 10% sample was somewhat harsher and the fabric showed good waterrepelient properties. Both the dry cleaning, and both samples retained their water-repel'lent properties after these tests. The

results on spun rayon were similar to those on cotton, except that the finish was livelier.

C. under reduced pressure gave a paste which.

hardened to a soft resin upon cooling and further I Example 2 Equimolecular quantities-ofbi guanide and so,- dium but'yl sebacate were dispersed in methanol,

thoroughly mixed, and allowed tostand. for sev-'- eral days until precipitation of the condensation product was complete. The solid material was oelerator. 80x80 cotton percaie filtered, washed with methanol, and dried. The

sodium salt of omega-carboxypelargonoguanae :mine was extracted from the condensation product with hot water-and precipitated by addition 1 of mineral-acid to a pH of about 4.0. After purification by solution in alkali and reprecipitation with acid apure product was obtained in the 1 form of a white solid melting at 223225' C'.

35 parts by weight of the omega-carboxy- 31% formalin and the mixture was heated to or t C. with continuous stirring.

original thick mixture became thinner and final-' -After 1.5 hours'the vlyhomogeneous. and upon stopping the agitator after 2 hours of heating the intotwo liquid layers.

; water-layer and drying the resin at reduced prespeilent properties.

mixture separated Upon decanting the thin sure a viscous gum was obtained Wh1Gh'WM 'SOI- ubie in sodium hydroxide. amineand other alkaliea' I '5 parts by weight of the resin were dissolved in partsof dilute ammonium hydroxide soluticn and cotton cloth was padded in the bath at prepared. The cloth wasthen squeezed until the resin content was 5% on the weight of the fiber and then placed in'a mordanting bath of aluminum sulfate to precipitate the aluminum salt on the fiber. The cloth was then dried in an oven whereupon it was found to possess good water re- Example 3 10 by weight of stearmmine parts of omega-carboxypelargonoguanamine were and 20 I combined with 46 parts of 31% formalin by the ammonia, 1 triethanolby a standard spray test. which is applied as folresin described I I Example 4 1.5156118 by weight. r

I in Example 1 were dissolved in methanol and emulsified in parts ofa solution containing 10 parts of the methyl ether of .trimethylol melamine, 0.6 part of isopropyl naphthalene sulfonate and 4.6

Cotton cloth impregnated -with these compositions. dried and cured also possessed good water-repellency.

Exempted .The hydrophobic properties of cloth treated'with higher alkyl guanamines in accordance withtho present invention were determined quantitatively dried and cured 10 inches from a horizontal terproofing agent, and then suspended spray nozzle supplied a head of exactly 6 feet. The for 1 minute, during which time water are discharged through the nozzle, drained for 10 seconds. rolled between pieces of absorbent paper to remove surface water, and again weighed. The increase in weight is expressed as ion to laundering,

per cent water absorbed. based on the original dry weight of the cloth. In order to measure samples ofv the treated cloth were washed in an 0.5% soap solution at 1". 30 minutes, rinsedand dried, and again subjected to the spray test. The samples were then dried 5 minutes etjaso'f' at 300'F. without the.

0.5% soap solution containing 0.2% of soda ash in an electric washat 160 8., followed by. I

1% andthe 10% sample showed good resistance to 'soaping and to the stearoguananiine capryloguanamine instead of A six-inch square of cloth treated with the wais weighed with waterat 10 1''. under cloth is sprayed 1 gallons of the resistance of the finwashed again for a total of 3.5 'hours. The

higher water absorption values of the first spray tests are explained by the presence of partially reacted resin components and accelerator on the cloth which would tend to absorb water.

The finished samples of cloth described in mample 4 were subjected to this test with the following results:

Example 6 An alkyd resin of high acid number (resin A) was prepared by the simultaneous reaction of 190 parts by weight of phath'alic anhydride, 101 parts of glycerine and 106.5 parts ofcottonseed fatty acids. After reacting these ingredients and holding for the desired viscosity the acid number of the resin was 60.

An alkyd resin of low acid number (resin B) was prepared by reacting 183 parts by weight of phthaiic anhydride, 100 parts of glycerine and 235 parts of castor oil at 425-450 F. until a resin having an acid number oi 6-3 was obtained. This resin was cut with 115 parts of butanol to 78% solids.

Resin A was cut to 80% solids by the addition of toluene and 67 .5 parts by weight of this 80% solution were taken. 163.5 parts by weight of the resin B solution were addedv and the mixture was warmed to 40 C. and stirred for. about 10 minutes, or until a homogeneous mixture was obtained. 35 parts by weight 01' the stearogua naminedormaldehyde resin of Example 1 were stirred into 274 parts by weight of a 50% solution of a butylated urea-formaldehyde resin in a mix= ture of equal parts of butanol and xylene and the resulting solution was then added to the alkyd resin solution and the mixture was cooled to 30 C. and stirred for an additional 10 minutes or until the entire mixture was homogeneous in character.

An ammonium caseinate solution was prepared in the following manner: 39 parts by weight of casein were soaked in 440 parts of water tor -3 hours at room temperature, or until the casein was sufiiciently swollen, and the mixture was then heated to 50430 C. to insure uniform hydration. After cooling to 40-50 C. an emmonium hydroxide solution was added in amounts suificient to obtain a uniform dis sion of the casein. Experience with emulsifying agents of this type has shown that amounts of 28% ammonium hydroxide ranging from to 26 parts by weight are satisfactory for this purpose, the exact amount depending upon the final pH desired in the finished emulsion. \After all the casein was dissolved by the ammonium hydroxide solution additional water was added to make a total of 505 parts by weight.

The mixture of high acid number akyld resin, low acid number alkyd resin, butylated ureaformaldehyde resin and stearoguanamine resin was agitated vigorously at C. and the solution of emulsifying agent was slowly added. Addition of the entire 505 parts of the emulsifier was made over a period of about 40 minutes,

after which agitation of the mixture was continued for an additional 30 minutes or until a, completely uniform emulsion was obtained. This emulsion was perfectly stable upon storage and could be easily diluted with water without separation.

All wool fabric was padded in a sizing bath containing 3 gallons of the above emulsion to 100 gallons of water. The impregnated fabric was dried under tension to prevent shrinkage for 7 minutes at 250 F. The dried fabric was found to possess the same softness as that of the original material, but was much firmer, and possessed good Water-repellent properties.

Equally good results were obtained when the butylated urea-formaldehyde wa replaced by an equal quantity of butylated melamine-formaldehyde resin prepared by condensing melamine with formaldehyde in the ratio of about 1:5 in the presence of an excess of n-butanol and heating with distillation of water until an anhydrous product is obtained.

Example 7 35.4 parts by weight oi phenyl biguanide and 60 parts by weight of methyl stearate were added to a solution of 4.6 parts by weight or sodium in 160 parts of methanol to which parts of the butyl ether of ethylene glycol (Butyl Cellosolve) had been added. The mixture was allowed to stand at room temperature for 24 hours after which it was evaporated to dryness at reduced pressure. The product was extracted with carbon tetrachloride, the solution evaporated to dry= ness, and the solids recrystallized from methanol.

The product was a, white crystalline solid which was identified as a-N-phenyl stearoguanamine.

A representative sample of the crystalline prodnot was converted into a resin by reaction with formaldehyde in the ratio of 5 moles oi aldehyde for each mole of the i N-phenyl stearogua namine. The reaction was carried out by dis-= solving the guanamine in methanol with the addition of heat, adding formaldehyde which had been neutralized to a pH of 8.0 and agitating for about minutes at C. The product had a melting point of (ii-65 0., and could be recrystallized from methanol as a definite methylol guanamine containing 0.6 mole of formalde hyde per mole of guanamine. The compound was found to be a plasticizer for urea-formalde hyde textile finishing compositions used for creaseproofing purposes, and was suitable for use in. admixture with such compounds Example 8 Ethyl beta-octadecoxy-propionate was pre= pared from octadecoxy propionitrile by refluxing the nitrile with concentrated sulfuric acid in the presence of ethanol for 7 hours. The prcdnot was purified by extraction with chloroform and filtration to remove ammonium sulfate and the filtrate was neutralized with sodium bicarbonate, washed with water and dried.

A mixture containing 92.5 parts by weight of the ethyl beta-octadecoxy-propionate, 25 parts of biguanlde, 400 parts of methanol, and 400 parts of ethanol was stirred at room temperature for 15 hours and then allowed to stand for 4 days. The resulting guanamine was removed by filtration and after recrystallization from acetone was found to have a melting point of 108-110" C.

A representative sample of the beta-octade-= coxypropionoguanamlne was converted to the methylol compound by reaction with 37% aque ous formaldehyde solution having a pH of 8.2

in the ratio of 6 moles of formaldehyde for each mole of the guanamine. The reaction was carried out in the methanol solution by heating the mixture at 70 C. for 45 minutes. The product when dispersed in water byt 'e addition of acetic acid was found to be an excellent waterproofing agent for cotton cloth, cellulose acetate cloth, and othertextile fibers.

A textile treatment bath was prepared containing 1.5 parts by weight of the above described guanamine resin and 10 parts by weight of a lower-primary alcohol-reacted melamine-formaldehyde resin. When cotton cloth was padded in this bath, dried, and cured at suitable temperatures it showed waterproofing properties comparable to those of the best waterproofed cotton fabrics now on the market.

Example 9 16.8 parts of 4-N-octanoyl-ootanoguanamine was stirred into a mixture of parts of 37% aqueous formaldehyde neutralized to pH 8 with triethanolamine, and 100 parts of isopropanol.

The mixture was heated to reflux, 100 parts of butanol were added, and the refluxing was continued for 40 minutes. After this time the isopropanol was distilled and the product was cooled and filtered to remove a small amount of uncombined guanamine.

- The filtrate was a clear syrup containing 18% of the octanoguanamine resin by weight. 100 parts of this syrup were dispersed in 1000 parts of an aqueous solution containing 10% of methylated methylol melamine, 5 parts of a mixture containing 88% diammonium phosphate and 12% of hexamethylene tetramine and 6% of sodium isopropyl naphthalene sulfonate. 80 x 80 cotton percale was padded in this solution, dried at 250 F. and cured 4 minutes at 300 F., after which treatment it was found to possess improved softness and water-repellency.

Example 10 Aminoacetoguanamine was prepared by reacting a solution of 70 parts by weight of glycine ethyl ester hydrochloride'in 200 parts of methanol, 13.8 parts of metallic sodium in 200 parts methanol, and a solution of 60.5 parts of higuanide in 175 parts methanol. The sodium methylate solution was first added to the glycine ester salt, the resulting sodium chloride filtered off, and the filtrate added to the biguanide solution.

68 parts by weight of stearyl chloride was dissolved in parts of dioxane and slowly added to a suspension of 28 parts of aniinoacetoguanamine in 200 parts of pyridine while maintaining the temperature below 20 C. The reaction mixture was allowed to stand for 5 hours and was then refluxed for one-half hour, after which it was poured into ice water and the product recovered and recrystallized. The stearylaminoacetoguanamine so prepared was a light tan solid which softened at 120 C. and was completely fused at 174 C. The product was condensed with formaldehyde, using 6 moles of 37% aqueous formaldehyde solution for each mole of the stearylaminoacetoguanamine. The formaldehyde was adjusted to a pH of 8.0 and added to a suspension of the guanamine in methanol and the mixture was heated to 75 C. and agitated at this temperature for 30 minutes. The resulting resin was applied as a water repellent to spun rayon challis. An emulsion was prepared in the man- 4-5 are mixed with about 100 nor previously described using 1.5% of the guanamine and 10% of methylated methylol melamine, based on the total weight of the solution, and 6% of curing accelerator, based on the amount of resin. After drying at 250 F. and curing for 4 minutes at 280 F. the cloth was soaped 30 minutes, rinsed and dried, and subjected to the spray test. It was found that only 39.6% of water was taken up by the fabric.

Example 11 123 .parts of 37% aqueous formaldehyde solution having a pH of 8.5 are mixed with parts of ethyl-n-butylacetoguanamine and the mixture is heated at 60-100 C. for 1-3 hours, thus producing a clear, aqueous syrup.

58 parts of 37% formalin having a pH of about parts of ethylisoamylacetoguanamine and heated under reflux at 7090 C. for about 3 hours, thereby producing a clear aqueous syrup.

100 parts of impure di-n-butylacetoguanamine and 68 parts of 87% formalin having a pH of 4-5 are mixed and refluxed at 60-90 C. until a clear syrup is obtained, requiring about 1-4 hours. Similarly other guanamines havin branched chain radicals containing at least 7 carbon atoms may be condensed with aldehydes such as formaldehyde in the same general manner as set forth in the above examples. Mixtures of the guanamines with melamine, urea, or mixtures of melamine and urea, when condensed with formaldehyde or other aldehydes produce resinous condensation products having desirable properties as the guanamines appear to exert a plasticizing action on the melamine and urea condensation products.

The aqueous resinous syrups prepared according to my invention have a" wide variety of applications in the treatment of textiles. They may cellulose derivatives such as cellulose acetate,

cellulose propionate, ethyl cellulose, etc. Dyes, lakes and pigments may be mixed with my guanamine-aldehyde condensation products and upon heating the mixture, insoluble materials are obtained. Furthermore, dyes, lakes and pigments, may be applied to substrata either before or after an application of a solution, dispersion or emulsion containing my guanamine-aldehyde condensation products. Upon application of heat, the dyes, lakes, or pigments are affixed to the substrata by means of the insoluble guanaminealdehyde condensation products.

Generally in .the treatment of textiles, it has been found preferable to use aqueous syrups containing my guanamine-aldehyde condensation products and if this be done, various water-soluble adjuncts may be admixed therewith, e. g., starch, gum tragacanth, the alginates, casein, etc.

Suitable softeners may be included in the com-,

my copending application Serial No. 33d,810, filed April 26, 1940.

What I claim 'is:

l. A method of finishing textiles which com prises the step of applying thereto a finishing agent containing a water-insoluble guanamine then heating the textiles to dry and set the finish.

on the fibers.

aliphatic radical containing at least seven carbon atoms, impregnating the textiles with said finishing composition, and heating the impregnated textiles to dry the same and set the finlshon the fibers thereof. I

9. A method of finishing textiles which com= prises the steps of preparing a liquid finishing composition comprising an aqueous dispersion of a water-insoluble guanamine in which the 2-car bon atom is connected by a carbon-to-carbori bond with an aliphatic radical containing at least seven carbon atoms, impregnating the textiles with said finishing composition, and heating the impregnated textiles to dry the same and set the finish on the fibers thereof.

10. A method of finishing textiles which com- I prises the steps of preparing an aqueous disper- 3. A method of finishing textiles which comprises the step of applying thereto a finishing agent containing a formaldehyde condensation product of a water-insoluble guanamine having a member of the group consisting of aliphatic and cycloaliphatic radicals containing at least seven carbon atoms directly attached to the 2-carbon atom thereof by a carbon-to-carbon bond and then heating the textiles to dry and set the finish on the fibers.

4. A method of finishing textiles which comprises applying thereto'a finishing agent containing a water-insoluble guanamine having a member of the group consisting of aliphatic and cycloaliphatic radicals containing at least seven carbon atoms directly attached to the 2-carbon atom thereof by a carbon-to-carbon bond together with a binder therefor and then subjecting the fibers to heating to set the finishing agent on the fiber.

5. A method of finishing textiles which comprises applying thereto a finishing agent containing a water-insoluble guanamine in which the 2- carbon atom is connected by a carbon-to-carbon bond with amember of the group consisting of aliphatic and cycloaliphatic radicals containing at least seven carbon atoms together with a curable heat-curing resin other than a guanamineformaldehyde resin and then heating the textiles to set the finishing agent thereon.

6. A method of finishing textiles which comprises applying thereto a finishing agent containing a water-insoluble guanamine in which the 2- carbon atom is connected by a carbon-to-carbon bond with a member 01 the group consisting of aliphatic and cycloaliphatic radicals containing at least seven carbon atoms together with a curasion containing a water-insoluble guanamine in which the Z-carbon atom is connected by a car= bon-to-carbon bond with an aliphatic radical containing at least seven carbon atoms, said dispersion also containing as an emulsifying agent a water-soluble guanamine containing an allphatic radical that is substituted by a member oi the class consisting of sulfonic and carboxylic acid groups, impregnating the textiles with said dispersion, and heating the impregnated textiles to dry th same and set the finish on the fibers 40 the 2-alky1 roup is a hydrocarbon chain conble heat-curing alkyd resin and then heating the insoluble guanamine in which the Z-carbon atom is connected by a carbon-to-carbon bond with an taining nine to seventeen carbon atoms and then heating the textiles to dry and set the finish on the fibers.

13. A method of finishing textiles which comprises the step of applying thereto a agent containing a formaldehyde condensation product of a 2-alkyl ge in which the 2-a1kyl group is a hydrocarbon chain containing at least seven carbon atoms and then heating the textiles to dry and set the finish on the fibers.

14. A method of finishing textiles which cornprises the step of applying thereto a finishing agent containing 9. formaldehyde condensation product of a Z-alkyl guanamine in which the .z-alkyl group is a hydrocarbon chain containing nine to seventeen atoms and then heating the textiles to dry and set the finish on. the fibers.

15. A method of ir textiles which comprises the step of applying thereto a finishing agent containing stearoguanamine and then heating the textiles to dry and set the finish on the fibers.

16. Textiles characterized by improved waterrepellency and having the individual fibers there of coated with a cured finishing composition containing a water-insoluble guanamine having a member of the group consisting of aliphatic and cycloaliphatic radicals containing at least seven carbon atoms directly attached to the 2-carbon atom thereof by a carbon te-carbon bond said textiles be lit. been finished by the method 01 JACK T. THURSTON.