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Publication numberUS3821023 A
Publication typeGrant
Publication dateJun 28, 1974
Filing dateDec 20, 1971
Priority dateDec 22, 1970
Also published asCA979157A1, DE2162620A1, DE2162620B2
Publication numberUS 3821023 A, US 3821023A, US-A-3821023, US3821023 A, US3821023A
InventorsAmati W, Hochreuter R
Original AssigneeSandoz Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Crease resistant finish for textiles having improved soil repellent properties
US 3821023 A
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Description  (OCR text may contain errors)

United States Patent 1191 1 Amati et a1. l t

[ June 28, 1974 CREASE RESISTANT FINISH FOR TEXTILES HAVING IMPROVED SOIL REPELLENT PROPERTIES [75] Inventors: Werner Amati, Prattcln/Bl; Richard Hochreuter, ()bcrwil/Bl, both of Switzerland 7 [73] Assignee: Sandoz Ltd., Basel, Switzerland [22] Filed: Dec.'20, 1971 21 Appl. No: 210,116

[30] Foreign Application Priority Data Dec. 22, 1970 Switzerland 18949/70 [52] US. Cl...ll7/139.5 A, ll7/l38.8 F, 117/139.4,

511 1m. (:1. .1 C08j 1/44 [58] Field of Search 117/1395 CQ, 139.5 R, 117/1395 A, 138.8 F, 138.8 B, 143 R,

[56] References Cited UNITED STATES PATENTS 1,935,264 11/1933 Felix .L 260/470 2,917,412 12/1959 Reinhardt et a1. 117/1394 UX 3,144,299 8/1964 Frick et a1. ll7/l39.4

Primary Examiner-William D. Martin Assistant Examiner-Theodore G. Davis Attorney, Agent, or Firm-Gerald D. Sharkin; Richard E. Vila; Thomas C. Doyle [5 7] ABSTRACT Compounds for the soil repellent finishing of textiles of the general formula wherein R stands for a p-valent radical of an organic compound which has one to 40 carbon atoms and contains at least one active hydrogen atom,

R for hydrogen or for a saturated orunsaturated alkyl or an aromatic radical or an aliphatic carboxylic acid radical which has one to 30 .carbon atoms or for the radical of an inorganic 14 Claims, No Drawings CREASE RESISTANT FINISH FOR TEXTILES HAVING IMPROVED SOIL REPELLENT PROPERTIES and where the molecule has a minimum molecular weight of 100 and bears at least one free acid group.

The p-valent radical R is the radical of a compound As is known, textiles of the various synthetic and cel- R(H),, having at least p active hydrogen atoms. which lulosic fibres, alone or in blends, in particular polyester fibre textiles, which have been finished with N- methylol resins, show enhanced power of soil retention whichmeans that they become heavily soiled in use and when washed cannot readilybe cleared of the impurities.

In order to overcome or diminish this undesirable behaviour, textiles of these fibres are finished with hydrophilic compounds. The products which have found acceptance in the textile industry for this purpose include the polyacrylic acid derivatives disclosedin US. Pat. No. 3,377,249, the polyoxyalkylene glycol terephthalic acid copolymers disclosed in French Pat. No. 1,502,969, the monostearic acid polyglycol esters disclosed in British Pat. No. 738,379 and the adducts of ethylene oxide and propylene oxide on alkyl phenols which are described in the published Swiss Pat. application 6149/68 and the published German Pat. application 1,914,389.

These products all have certain disadvantages. The polyacrylic acid derivatives impart a harsh, stiff handle to the finished fabric, the polyoxyalkylene glycolterephthalic acid copolymers are not applicable to cotton, while the monostearic acid-polyglycol esters, and the ethylene oxide and propylene oxide adducts on alkyl phenols leave the fabric with unsatisfactory wash resistance and impair the fastness properties .of dyed goods, especially if they have been dyed with disperse dyes.

It has been found that these disadvantages are absent when compounds of formula (1) below are used for the soil repellent finishing of textiles, in combination with a resin, for example one of the resins used for crease resistant finishing, while the soil repellency thereby obtained is greater than that given by the aforestated compounds.

This invention therefore relates to the use for the soil repellent finishing of textile fibres, yarns and fabrics of compounds agreeing with the general formula where R stands for a p-valent radical of anorganic compound which has oneto 40 carbon atoms and contains at least one active hydrogen atom,

R for hydrogen or for a saturated or unsaturated alkyl or an aromatic radical or an aliphatic carboxylic acid radical which has 1 to 30 carbon atoms or for the radical of an inorganic acid which may be esterified,

m for the value 2, 3 or 4,

n for zero or a value from 1 to 100,

y for zero or the value 1,

p for a value from 1 to 4 X i for -NH- or where Z is a lower alkyl radical may be present in the form of hydroxyl (-OH) groups or bound on a carbon atom. Alternatively, the -OH group or -NH grouping may be bound to a partially esterified acid group, for example -PO L ')OH, where the preferred meaning of L is that of an optionally substituted alkyl or alkenyl radical having one to 30 carbon atoms.

The p-valent radical R consists of an optionally further unsubstituted or substituted alkyl, alkenyl or aromatic radical having one to 40 carbon atoms, these atoms bearing at least one of the aforenamed alcoholic, thioalcoholic, acid or amidated groups which is capable of binding an active hydrogen atom. The preferred unsubstituted or substituted alkyl radicals have one to 40 carbon atoms, special preference being given to aliphatic hydrocarbon radicals with two to 22 carbon atoms which may bear aromatic ring systems as substituents. The substituents on the alkyl radicals are preferably phenyl, naphthyl, diphenyl, diphenylether, diphe nylsulphide or diphenylmethane radicals, which may be further substituted by hydroxyl, lower alkyl or an acid radical.

Besides the distinctive feature of being monomeric in character and bearing at least one free acid group, the v disclosed compounds are further characterized by the fact that the value of it may vary within wide limits. Compounds with high n values are of major interest for the finishing of white goods. In these, the introduction of several free acid groups, in particular carboxymethyl groups or phosphorus or sulphonic acid groups which may if desired by esterified, has a favourable effect. Given low n values, it is of advantage to introduce hydrocarbon radicals of high molecular weight.

Notably good results are obtained when the following R radicals are employed:

000 QOO ([100...

COOH

(l300 (13OO- COO- 1 COOH HOOC ooo cm-0- 94 04 The radicals -C H11 C, H

-C H -C l-l -SO H, -PO H and -CH COONa and also the homologous series of C H to C I-l radicals are highly suitable as R radicals, and given certain conditions those named as meanings ofR are also ofinterest.

The compounds of this invention contain at least one but preferably not more than five free acid groups, which may be present as alkali-metal or ammonium salts. Optimally one to three acid groups are present.

The compound of formula I should have a minimum molecular weight of 100.

The compounds employed in accordance with this invention can be produced by known methods or in analogy with known methods, with the necessary condition that one free acid group remains in the reaction product or is introduced into it. A number of these methods are outlined below.

a. Reaction of a sulphonated or unsulphonated aliphatic or aromatic carboxylic acid or a carboxylic acid derivative with an aliphatic alcohol or with an alkyl, aryl or alkylaryl polyglycolether at elevated temperature.

b. Esterification of an unsaturated monocarboxylic or polycarboxylic acid or a derivative of such an 'acid with an alcohol or with alkyl, aryl or alkylaryl' polyglycol ether at high temperature, if necessary with the aid of a catalyst, with subsequent addition of e.g. sodium sulphite or sodium hydrosulphite in aqueous solution.

Reaction of a polycarboxylic anhydride with an aliphatic alcohol or an amine and subsequent esterification of a carboxylic acid group with a polyglycol in the presence of catalyst to yield the diester.

d. Reaction of a compound bearing hydroxyl groups with an inorganic acid as phosphoric or sulphuric acid or an acid derivative such as polyphosphoric acid, phosphorus pentoxide, phosphorus oxychloride, phosphorus acid, phosphorus trichloridc, sulphur trioxidc, halogenosulphonic acid, in the ab- @LCOOH, @mmm,

sence or presence of an inert solvent, to yield the corresponding acid ester.

e. Alkylation of phosphoric or phosphorus acid or their salts.

f. Reaction of aromatic polycarboxylic acids or their derivatives with a polyglycol at elevated temperature, with subsequent esterification of one of the free carboxylic acid groups with an aliphatic alcohol in the presence of catalyst.

h. Addition of alkylene oxide on inorganic carboxylic acids, amines, monovalent or multivalent alcohols in the presence of an alkaline catalyst, and subsequent reaction of the terminal hydroxyl groups with a halogen acid or an unsaturated a,,B-carboxylic acid, e.g. monochloracetic, acrylic, crotonic or methacrylic acid, in the presence of sodium hydroxide at elevated temperature.

i. Addition of epichlorohydrin on polyglycols at high temperature in the presence ofa Lewis acid as catalyst, subsequent cleavage of hydrogenchloride by the addition of sodium hydroxide, reaction of the resulting diepoxide with ammonia or an amine, and finally alkylation with monochloracetic acid in aqueous solution with the addition of alkali.

The starting products named in the following can be used to produce compounds conforming to this invention.

The carboxylic acids may be saturated or unsaturated, aliphatic or aromatic monoor p0ly-carboxylic acids, preferably polycarboxylic and/or sulphocarboxylic acids, or their derivatives such as the anhydrides, esters or halides, notably the chlorides or bromides. Of the saturated dibasic acids may be named oxalic, malonic, succinic, adipic and azelaic acid; of the unsaturated dibasic acids maleic and fumaric acid; of the hydroxyl-substituted acids maleic, tartaric and citric acid; of the aromatic dicarboxylic acids phthalic, isophthalic and terephthalic acid; of the aromatic tricarboxylic acids trimellitic, hemimellitic and trimesic acid; of the aromatic tetracarboxylic acids mellophanic and pyromellitic acid; and as hexacarboxylic acid mellitic acid. Further, mention may be made of diphenyldicarboxylic acid, aliphatic and aromatic sulphocarboxylic acids, sulphuric acid esters such as sulphosuccinic and sulphotricarballylic acid, the sulphation products of fatty acids such as oleic acid, sulphuric acid esters of monoand di-oxystearic acid, sulphobenzoic, sulphophenylacetic, sulphophenoxyacetic and sulphophthalic acids, sulphophthalic acid amides, naphthalenesulphonic and naphthalenepolysulphonic acids and their alkyl derivatives in which the alkyl chains bear one to 24 carbon atoms, alkanc and alkene acids having preferably eight to 30 carbon atoms, for example caproic, caprylic, cypric, lauric, myristic, stearic, arachic, be-

henic, oleic and ricinoleic acid, the corresponding sulphonic acids, the sulphates of the corresponding alcohols, aromatic monocarboxylic and monosulphonic acids such as phenolcarboxylic acids (salicylic acid), phenolsulphonic acids. their condensation products with formaldehyde, mono-, diand tri-alkylphenolsulphonic acids, alkylphenylphosphoric acid esters such as amyl and diamyl derivatives, nonyl derivatives, dodecyl and octadecyl derivatives.

For esterification, saturated or unsaturated hydroxy compounds having preferably six to 30 carbon atoms are suitable, examples being octyl, lauryl, stearyl, behenyl, oleyl and bezyl alcohol, phenols, naphthols and their alkylation products, ethylene and propylene adducts from the aforenamed compounds which have one to 90, preferably one to 60, alkylene oxide units.

Of the polyglycols and copolymers of polyethylene and polypropylene oxide, the compounds having a molecular weight of about 200 to 6,000 deserve special mention.

To exemplify the starting materials used to form the organic derivatives of phosphoric or phosphorous acid, notably their esters from the corresponding alcohols or polyglycol derivatives, the following may be named: phosphoric and polyphosphoric acid, phosphorus pentoxide, phosphorus oxyhalides, phosphorus trihalides and phosphorous acid.

The suitable sulphonating agents include sulphuric acid, sulphur trixode, chlorosulphonic acid, bisulphite and sulphur dioxide, in the presence of chlorine or oxygen. v

The resins applied in conjunction with the disclosed compounds are preferably aminoplasts, which impart a crease resistant finish to textile substrates. As a rule, N-methylol urea or M-methylol melamine compounds can be used for this purpose with good success. Examples of formaldehyde and methylol resins of this type are the derivatives of compounds of formula NH I O=O\ A1 where A represents a radical of formula A; 4311-0112- -ArCH-OCHA -CHT-CH2-, -CH;-( HCH A r-O CH3 CH3 and A represents hydrogen or lower alkyl. Other suitable resins are urea, melamines, e.g. tri-, tetra-, pentaand hexa-methylol melamine, carbamates, formaldehyde-acrolein and formaldehydeacetone condensation products, alkylolamides, e.g. methylol formamide, methylolacetamide, acrylamides, e.g. N- methylolformamide, N-methylolmetacrylamide, N-methylmethylolacrylamide, diureas, e.g. trimethylol and tetramethylol acetylene diurea, triazones e.g. dimethylol-N-ethyltriazone, haloacetamides, e.g. N- methylol-N-methylchloracetamide, urones, e.g. dimethylolurone and dihydroxydimethylolurone, and mixtures of these resins. The resin finishing of textiles is carried out preferably in the presence of catalysts. The salts of multivalent metals with strong mineral acids, ammonium and amine salts and acids are used as catalysts for the reaction of N-methylol compounds. The suitable salts include the magnesium and zinc nitrates. phosphates and halides, zinc oxychloride, combinations of boric acid and calcium chloride, acetates. e.g. of zinc or magnesium. Ammonium sulphate, chloride and bromide are suitable ammonium salts; monoammonium and diammonium phosphate and alkanolamino hydrochlorides such as mono-. diand triethanolamino hydrochloride can also be used.

Examples of suitable acids are hydrochloric, sulphuric and phosphoric acid, but preference is given to lower aliphatic acids such as propionic, glycolic, lactic, tartaric, citric and oxalic acid, and in particular formic or acetic acid, either alone or in combination with the aforestated metal salts. Also suitable are succinic, maleic, sulphanilic and other acids. These acids can be used alone or in combination.

The compounds of this invention: are applied to textile substrates in combination with a resin, preferably one of the aforenamed N- methylol resins, and a catalyst. They are applicable to natural cellulosic (cotton, linen, hemp) and regenerated cellulosic fibres (viscose and cuprammonium rayon, polynosic and high wet modulus fibres), polyester, polyacrylonitrile, polypropylene, polyamide and other synthetic fibres, including blends of these fibres. They are of special interest for finishing cotton and polyester textiles. The substrate may be present as loose fibre, yarn, woven or knit fabric, carpeting, felts or nonwovens, or in other textile forms.

The compounds of formula (I) are applied to the high-polymer textile substrates in combination with optionally precondensed resins from aqueous-organic or preferably aqueous medium using the known methods. It is preferable to employ the said compounds and resins in the form of preparations which may contain, for example, 10 to 90 percent of a compound of formula (I) and 10 to 90 percent resin, though the optimum ratio of the compound to the resin is :30 to l0z90. Any of the standard methods of application is employable by means of which the preparations, if necessary after prior dilution, can be deposited on the substrate, for example padding, spraying, coating, dipping, printing, screen or foam application. It is desirable for the substrate to be finished with 0.01-10 percent or preferably 0.1-3 percent (relative to its weight) of the selected compound of formula (I) in combination with the resin. After intermediate drying (if necessary for the method used) the textiles are dry heat treated for fixation of the finish.

A suitable technique for applying the products of this invention jointly with N-methylol type resins is as follows. 50-300 or preferably 200-250 parts by weight of an approximately 50 percent aqueous solution of the N-methylol compound, which may if desired be partially condensed, are mixed with 20-300 or preferably 100-200 parts by weight of an almost neutral (pH-- 6-7), approximately 25 percent aqueous solution or dispersion of acompound of this invention, with the addition of 5-75 or preferably 20-30 parts by weight of one of the aforecited catalysts. The solution or dispersion is diluted to 1,000 parts with water. It is padded on fabric at 50l50 C or preferably -l00 C and an expression giving an increase of 50-80 percent or preferably 70-75 percent on the dry weight, if necessary at reduced pressure or in an inert gas atmosphere. The fabric is treated in dry heat at -220 C or preferably -l80 C for l-lO or preferably 2-6 minutes to fix the finish, rinsed with water and dried.

The finish thus produced imparts durable soil repel- 25 1= m as H Example 7 d t d U ates th II l2 R '-'C5H4'C9H|9 R; H Example 70 lency an crease I'CS'IS-EIHCC an grea y n: 30 RI C6H4,C9HI9 R: H Example removal of SOll and Oil in wash baths. Textile fabrics finn R C H R C H Example 12 ished on these lines with products as disclosed herein have a soft handle, show a very good antistatic effect 6 R O(CH CH O),,CH COONa and, when dyed, undergo no loss or only minimal loss in the colour fastness properties In the following Examples, which illustrate the inven- 2f 2 g 2: 3 35 tion without hmltlng its scope, the parts and percent- R c u co n 6 Example 81 ages are by weight and the temperatures in degrees g l g gg g;

. cent grade. The products used in the Examples are i R hi 6,8 gxamgle 3e specified in the preceding table. R C H g8 n l 3.5 Example gf 1. General formula of the compounds listed in Table R 3 l.

[5 7. CH2(OCHzCHz)mOOHzC0ONn COO(CH2CH2O)|1R CH-(OCHaCHzMOCHzCOONa I oHz-(ocHgoHmocHzoooNa IO COER] m+n+p= l5 ExampleQ m n p 60 Example 9a m n p= 120 Example 912 EL. 3? m n p 9 Example 9c Table 1 R R, R2 R;, E n Example C H H cooH H 0 40 1 c H H cooH cooH 0 la m aa H H H O 40 lb CGH;C,H.;, H COOH H 0 10 I0 H H H 0 25 Id I C 4 H H H 0 60 le C H H H H 0 10 If C H H COOH COOH o 25 lg H CHHM COOH H o 2 H c.,H COOH H 0 13.5 2a H CHHMCONWCHM COOH H 0 13.5 2b so H B COOH H 0 I35 3 so H C H H H 0 23 3a SOHH COOH H NH 45 3b PO H 3? COOH H 0 13.5 4 Po H CWHH, H H 0 23 4a Po H c H cooH H NH 45 4h C,,H H so H H 0 0 l 1 CmH-17 H SO H H 0 lla H QS H so H H 0 25 He C H H SO H H 0 0 lid lB 35(OCH2 2)n C C (CH2CH20)nCisI-Ia5 8. N300CCH2NIICH2?HCH2(OCH2OH2) OCH2$II 45 OH OH 1-1000 COOH CHeNHCHaCOONa 25 Example n 45 Example 10 n 40 Examp|e n 23 Example 10a n 135 Example lOb n 6,5 Example 10- a.

-coo on2om0 n0o CO0R nooc- H EXAMPLE I 38.4 Parts (0.2 mol) of trimellitic anhydride and 406 23 R Cm17 Exampk 5 parts (0.2 mol) of oleylpolyglycol ether having 40 ethn= 13.5 t H p e ylene oxide groups are reacted for several hours at 150l60? with stirring until the acid number reaches CmcOOwHCHEOMCQH the value calculated for 0.4 equivalents. The trimellitic Z)m acid ester'thus formed is a yellowish brown wax-like omooon product. It dissolves readily in water and shows notably good soil repellent and antistatic properties. I "=40 m l R =OH R =COOH Example 6 Products with com arabl ood ro e ties a "=25 m=l RI=0H R:=COOH Example6a d h l re Ob 40 m 2 R H R2: H Example ame w en, in p ace 0 trrme me an y r1 e, 35 2 H R2 H Example 60 la. pyromelhtic dianhydrlde or lb. phthalic anhydride 5. onto 00(CH:oH20).,Rt are employed, or when in place of oleylpolyglycol ether with 40 ethylene oxide groups 1c. nonylphenylpolyglycol ether with ethylene oxide groups, or in place of trimellitic anhydride and oleylpolyglycol ether with 40 ethylene oxide groups 1d. phthalic anhydride and oleylpolyglycol ether with ethylene oxide groups,

1e. phthalic anhydride and phenylpolyglycol ether with 60 ethylene oxide groups,

if phthalic anhydride and phenylpolyglycol ether with 10 ethylene oxide groups,

lg. pyromellitic dianhydride and oleylpolyglycol EXAMPLE 2 192 Parts (1 mol) of trimellitic anhydride and 270 parts (1 mol) of stearyl alcohol are reacted at 150-160 for several hours with stirring until the acid number reaches the value calculated for 2 equivalents. 231 Parts (0.5 mol) of the trimellitic acid stearyl ester thus formed are dissolved in 1,000 parts (0.5 mol) of polyethylene glycol, molecular weight 2,000, 0.5 part of concentrated sulphuric acid and 200 parts of xylene in a sulphonation vessel fitted with a water separator. The solution is brought to the boil with thorough stirring and boiled with reflux until no further water separates out and the acid number approximates to the calculated value. The solvent is then evaporated, leaving as residue the trimellitic acid diester. In the form of the sodium salt this product has good water solubility and is highly suitable for the soil repellent finishing of textiles.

Products of similarly good quality are obtained when the stearyl alcohol and polyglycol of molecular weight 2000 are replaced by 2a. lauryl alcohol and polyethylene glycol of molecular weight 600, or

2b. N-stearoylaminoethyl alcohol and polyethylene glycol of molecular weight 600.

EXAMPLE 3 A solution of 192 parts (1 mol) of trimellitic anhydride, 270 parts (1 mol) of stearyl alcohol and 600 parts 1 mol) of polyethylene glycol, molecular weight 600, is reacted in analogy with the preceding Example. 104 Parts (0.1 mol) of the resulting trimellitic acid diester are dissolved in 200 parts of carbon tetrachloride, after which 23 parts (0.15 mol) of phosphorus oxychloride are added The solution is held at 60 until the cal- 55 culated amount of hydrogen chloride gas has escaped, upon which the solvent is evaporated and water added to hydrolyse the residue to the phosphoric acid ester. The product thus obtained is well soluble in water and is especially suitable for combined application with N- methylol compounds to produce durable soil and oil repellent finishes on textiles; these finishes impart a soft handle to the textiles and a very good antistatic effect. Moreover they have no adverse effect on the fastness properties of dyed goods.

Products with similarly good properties are obtained when in place of polyethylene glycol of molecular weight 600 and trimellitic anhydride 3a. polyethylene glycol (molecular weight 1000) and phthalic anhydride. or in place of stearyl alcohol and polyethylene glycol (molecular weight 600) 3b. stearyl amine andpolyethylene glycol (molecular weight 2.000) are used.

EXAMPLE 4 104 Parts (0.1 mol) of the trimellitic acid diesterobtained as intermediate in Example 3 are dissolved in 200 parts of carbon tetrachloride, with the subsequent dropwise addition of 1 1.7 parts (0.1 mol) of chlorosulphonic acid. The solution is maintained at 60 until the calculated amount of hydrogen chloridegas has escaped, then the solvent is evaporated. The sulphuric acid ester thus formed is well dispersible in water and is excellent for soil repellent finishing, having compara bly good properties to the products obtained by the 20 procedure of Example 3.

Further products with equally good properties can be produced by using in place of polyethylene glycol (molecular weight 600) and trimellitic anhydride 4a. polyethylene glycol (molecular weight 1,000)

and phthalic anhydride or in place of stearyl alcohol and polyethylene glycol (molecular weight 600) 4b.- stearyl amine and polyethylene glycol (molecular weight 2,000).

EXAMPLE 5 A solution of 296 parts (2 mols) of phthalic anhydride and 1,000 parts (1 mol) of polyethylene glycol, molecular weight 1,000, is held at 160180 until the acid number reaches the value calculated for 2 equivaboil and held at this temperature long enough for the calculated amount of water to be distilled and the acid number to reach approximately the theoretical value. The solvent is then removed by distillation. A soft, waxlike product of beige colour is obtained when in the form of the sodium salt is readily soluble in water and shows particularly good soil repellent and antistatic properties.

1n place of polyethylene glycol (molecular weight 1,000) and stearyl alcohol 5a. polyethylene glycol (molecular weight 600) and octanol can be employed, on which a product with comparable properties is formed.

EXAMPLE 6 A solution of 19.2 parts (0.1 mol) of citric acid, 203 parts (0.1 mol) of oleylpolyglycol ether with 40 ethylene oxide groups, 0.2 part of p-toluenesulphonic acid and 150 parts of xylene is set for reaction in a vessel equipped with stirrer and water separator. It is raised to the boil and held at this temperature until the acid number reaches the calculated value. After removal of the solvent by distillation, a pale, wax-like product of 7 soft texture is obtained which is well soluble in water and is highly suitable for the soil repellent finishing of textiles.

1 Other products with comparable properties can be obtained by using in place of oleylpolyglycol ether with 40 ethylene oxide groups 6a. oleylpolyglycol ether with 25 ethylene oxide groups or in place of citric acid 6b. adipic acid or in place of citric acid and oleylpolyglycol ether with 40 ethylene oxide groups 60. adipic acid and oleylglycol ether with 25 ethylene oxide groups.

EXAMPLE 7 A solution of 19.2 parts (0.2 mol) of maleicanhydride and 274 parts (0.2 mol) of oleylpolyglycol ether with 25 ethylene oxide groups is reacted at 130-l50 until the acid number reaches the theoretical value. A solution of 25.2 parts (0.2 mol) of sodium sulphite in 100 ml of water is added, after which stirring is continued for 2 to 3 hours at 80. The iodine consumption of a sample drops virtually to zero after this time. A 25 percent aqueous solution is obtained which has very good soil repellent and antistatic properties.

Products with equally good properties can be obtained by substituting for oleylpolyglycol ether with 25 ethylene oxide groups 7a. nonylphenylpolyglycol ether with 12 ethylene oxide groups or 7b. nonylphenylpolyglycol ether with 30 ethylene oxide groups.

EXAMPLE 8 The solution for reaction is prepared with 137 parts (0.1 mol) of oleylpolyglycol ether having 25 ethylene oxide groups, 11.6 parts (0.1 mol) of the sodium salt of monochloracetic acid, 4 parts of sodium hydroxide, 0.16 part of sodium carbonate and 0.6 part of water. It is reacted for 5 hours at 100, during which time the acid consumption of a sample decreases practically to zero. The product is readily soluble in water and has notably good power of soil repellency.

Other products showing comparable properties can be produced by using in place of oleylpolyglycol ether with 25 ethylene oxide groups 8a. oleylpolyglycol ether with 40 ethylene oxide groups,

8b. lauric acid polyglycol ester with 6.8 ethylene oxide groups,

8c. lauric acid polyglycol ester with 13.5 ethylene oxide groups,

8d. lauric acid polyglycol ester with 23 ethylene oxide groups,

8e. stearic acid polyglycol ester with 6.8 ethylene oxide groups,

8f. stearic acid polyglycol ester with 13.5 ethylene oxide groups,

8g. stearic acid polyglycol ester with 23 ethylene oxide groups.

EXAMPLE 9 In analogy with Example 8, a solution of 150 parts (0.2 mol) of glycerotripolyglycol ether having three times 5 ethylene oxide groups, 70 parts (0.6 mol) of the sodium salt of monochloracetic acid, 24 parts (0.6 mol) of sodium hydroxide, 1 part of sodium carbonate and 5 parts of water is reacted to yield a yellowish product which is well soluble in water. It is highly suitable for the soil repellent and antistatic finishing of textiles.

Further products with similarly good properties are obtainable by using in place of glycerotripolyglycol ether containing three times 5 ethylene oxide groups,

9a. glycerotripolyglycol ether with three times 20 ethylene oxide groups or 9b. glycerotripolyglycol ether with three times 40 ethylene oxide groups.

EXAMPLE 10 A solution of 500 parts (0.25 mol) of polyethylene glycol, molecular weight 2,000. 46.2 parts (05 mol) of epichlorohydrin and a small amount of borotritluoroetherate is reacted in the known manner to form the dichlorohydrin ether. A solution of 20 parts (0.5 mol) of sodium hydroxide in 20 parts of water is added to convert the ether into the diepoxide. The separated sodium chloride is removed by filtration and the diepoxide dropped into 250 parts of 25 percent ammonia at room temperature for conversion into the diamine. When the end-point of the reaction is reached the batch is evaporated to dryness. A clear brownish product is obtained in a yield of 481 parts, its content of diamine (determined by filtration with perchloric acid) being approximately percent.

A solution of 42.8 parts (0.02 mol) of the diamine, 4.7 parts (0.04 mol) of the sodium salt of monochloroacetic acid, 1.6 parts of sodium hydroxide and 147.3 parts of water is reacted for several hours at about the reaction being terminated when the sulphuric acid consumption of a sample drops to nil. A clear pale yellow solution is obtained. The product is a very effective agent for the soil repellent finishing of textiles.

The polyethylene glycol of molecular weight 2,000 can be replaced by 10a. polyethylene glycol of molecular weight 1,000,

10b. polyethylene glycol of molecular weight 600 or 100. polyethylene glycol of molecular weight 300;

or again the molar ratio of the chosen polyethylene glycol of molecular weight 300-2,000 to the sodium salt of monochloracetic acid can be changed from 1:2 to a ratio between 1:4 and 1:6, upon which products with comparable properties are formed.

EXAMPLE 1 l EXAMPLE 12 A solution of 49 parts (0.5 mol) of maleic anhydride, 270 parts (0.1 mol) of stearyl alcohol, 0.5 part of p-toluenesulphonic acid as catalyst and parts of toluene as decelerating agent is prepared in a sulphonation vessel titted with a water separator. It is reacted for 5 hours at boiling temperature with reflux, during which time 8 millilitres of water is collected while the acid number decreases practically to zero.

A solution of 248 parts (0.4 mol) of the resulting maleic distearyl ester, 106 parts (0.416 mol) of a 41 per It is an excellent soil repellent agent for textiles and does not impair the fastness of disperse dyeings to any appreciable extent.

APPLICATION EXAMPLE A A blend fabric of 67 percent polyester fibre and 35 percent cotton is padded with an aqueous dispersion containing 250 g/l of 50 percent aqueous dimethylol dihydroxyethyl urea, 25 g/l of Zn(NO -6l-1 O and 200 g/l of the 25 percent aqueous (pH 6.5-7) product of Example 1, the expression on the padding machine giving a 75-80 percent increase on the dry weight. The fabric is dried at 120 and dry heat treated for 5 minutes at 160 for fixation of the finish. It is then cut into two halves. The first half is washed once and the second five times for 30 minutes at 60 with a commercial detergent. The two samples are then submitted to the tests described below.

a. Oil spotting test The sample is spotted with used automobile oil, washed and assessed for ease of oil removal. b. Soil deposition in washing The sample is washed, dried and washed again in a wash bath set with 6 g/l of a fully active detergent and 5 g/l of an artificial soil mixture consisting of 38 peat l7 cement l7 china clay diatomaceous earth 0.5 Zn ferric oxide automobile oil gas soot flame soot The degree of greying due to deposition of these impurities on the fabric in washing is assessed.

APPLICATION EXAMPLE B A fabric of 67 percent polyester fibre and 33 percent cotton is padded at a liquor pickup of 75-85 percent with a liquor containing 250 g/l of percent aqueous dimethylol methylcarbamate, 25 g/l of'zinc chloride and 200 g/l of the 25 percent aqueous (pH 6.5-7) prod uct of Example 4. After drying at 120 the finish is fixed by dry heat treatment for 5 minutes. The fabric is cut in two and the two samples tested for soil repellency and soil deposition in washing by the methods given in the preceding Application Example.

APPLICATION EXAMPLE C A fabric of 67 percent polyester fibre and 33 percent cotton ispadded at a liquor pickup of -85 percent with a liquor containing 250 g/l of 50 percent aqueous dimethylol propylene urea, 25 g/l magnesium chloride and 200 g/l of the 25 percent aqeuous (pl-1 6.5-7) prod uct of Example 10. The fabric is dried at and the finish thermofixed for 5 minutes at It is then halved and the two samples tested as in Application Example A for soil repellency and soil deposition or greying in wash baths.

in the following table the test results are evaluated on a numerical scale from 1 to 5, where 5 represents excellent and 1 poor behaviour in the test. The two synthetic resins referred to in the first column of the table are di methyl dihydroxy ethylene urea (I) and dimethylol propylene urea (11).

Qil spotting test Soil deposition in washing Loss of fastness Type of finish After one After five After one After five Fabric handle by disperse wash washes wash washes dyeings Synth. resin 1+ Prod. 1 3-4 3 5 2 soft Synth. resin 1+ Prod. 11: 3 3 4 2 Synth. resin 1+ Prod. lb 3-4 3 5 Z Synth. resin 1+ Prod. lc 3 3 4 2 Synth. resin 1 Prod. 1d 3 3 4 2 Synth. resin 1 Prod. 1e 3-4 3-4 4 2 Synth. resin 1+ Prod. 1f 3 3 3 1 Synth. resin 1+ Prod. 1g 3-4. 3 4 2 Synth. resin 1+ Prod. 1h 4 3 4 2 Synth. resin 1+ Prod. 1i 4 4 4 3 Synth. resin 1+ Prod. 2 3 3 5 3 Synth. resin 1 Prod. 2a 3-4 3-4 5 2 Synth. resin 1 Prod. 2b 3 3 5 2 Synth. resin 1+ Prod. 3 34 2-3 4 2 Synth. resin 1+ Prod. 3a 4 3 4 2 slight Synth. resin 1+ Prod. 3b 4 3 4 3 slight Synth. resin 1 Prod. 4 3 3 5 3 soft slight Synth. resin 1 Prod. 40 3-4 3 5 3 soft slight Synth. resin 1 Prod. 4b 2-3 3 4 3 soft Synth. resin 1+ Prod. 5 3 34 4 2 soft Synth. resin 1+ Prod. 5a 3 3 4 2 soft Synth. resin 1+ Prod. 6 3-4 4 4 3 soft Synth. resin 1 Prod. 6a 34 3 3 2 soft Synth. resin 1 Prod. 6b 4 34 5 3 soft. Synth. resin 1 Prod. 6c 3 3 4 2 soft Synth. resin 1 Prod. 7 3-4 3 4 2 soft Synth. resin 1+ Prod; 711 34 3-4 4 2 soft Synth. resin 1 Prod. 711 3-4 3-4 4 2 soft Synth. reain 1+ alkylphc- 3 3 l 1 soft marked nylpolyethylene glycol ether Synth. resin 1+ polyncry- 4 3 4 l stiff. harsh late product Synth. resin 1 alone 3 2 1 1 stiff. rough Synth. resin 11+ Prod. l 4 2 5 3 soft Synth. resin 11+ Prod. 2 4 2 4 3 soft Synth. resin 11 Prod. 2a 4-5 2 3 2 soft Synth. resin 11 Prod. 2b 4 2 4 3 soft Synth. resin 11+ Alkylphe- 4-5 1-2 4 2 marked ylnq x yl neslx ether.

soft

Oil spotting test Soil deposition in washing Loss of fastness Type of finish After one After five After one After five Fabric handle by disperse wash washes wash washes dycings Synth. resin ll Polyacr- 4-5 [-2 3 stiff. harsh ylate product Synthv resin ll alone 3 2 l l rough, stiff Synth. resin l+ Prod. ll 34 3-4 4 2 soft nil Synth. resin l+ Prod. I la 3 3 5 2 soft slight Synth. resin Prod. llb 3-4 3 4 2 soft slight Synth. resin l Prod. l2 3 3 4 2 soft slight Comparative tests without a product of the disclosed type.

Having thus disclosed the invention, what we claim the formula f' f f ,Lm fi i where R is a p-valent radical of an organic compound which has one to 40 carbon atoms and contains at least one active hydrogen atom,

R is hydrogen or a saturated or unsaturated alkyl or an aromatic radical or an aliphatic carboxylic acid radical which has one to 30 carbon atoms or the radical of an inorganic acid,

m is 2, 3 or 4 n is zero or 1 to 100,

y is zero or 1,

p is 1 to 4, and

X is -NH- or COO wherein B is hydrogen or an alkali-metal ion and d is l or 2,

R is an alkyl radical which has eight to 30 carbon atoms,

n is zero or 1 to 10,

y is zero and p is l.

3. A process according to claim 1 wherein in compound (c) R contains one to 40 carbon atoms and is an alkyl, alkenyl or phenyl radical bound to the remainder of the compound of formula (I) through p groups capable of binding an active hydrogen and selected from -O-, -S-,

wherein L is alkyl or alkenyl of one to 30 carbon atoms, said R, when alkyl, being unsubstituted or substituted by phenyl, naphthyl, diphenylether, diphenylsulphide or diphenylmethane, and

R is a member of the group consisting of hydrogen,

-C18H35, -CH2CH2COONE, C6H4'C9H 9, -SO3H, -PO H -CH COONa and can, wherein q is eight to 18.

4. A process as in claim 1 wherein the textile material consists of cellulosic fibers, synthetic fibers, or mixtures thereof.

5. A process according to claim 1 wherein the textile material is dried following the application of the aqueous dispersion and prior to the fixation step.

6. A process as in claim 1 wherein the compound of formula (I) is used in amounts of0.0l to 10 percent relative to the weight of the substrate.

7. A process as in claim 6 wherein the compound of formula (I) is used in amounts of 0.1 to 3 percent.

8. A process according to claim 3 wherein the com pound (a) is a methylol urea, 21 methylol melamine, a methylol carbamate or a methylol trizonc.

9. A process according to claim 6 wherein compound (0) is of the formula COO- (G oooo n coon,

CO COO- COER] onncnmr,

00011 cg HOOC/ ""co'o ooc co0 '0 00011, 11000 0 coon, X/ HOOC COOH COOH OaH where CH: COO EHIO ZH:-O R is hydrogen or a saturated or unsaturated alkyl or H S o C =-o-, H-O,

. a- H-0ooH, aliphatic carboxyllc acid radical WhlCh has one to Hg-0- v 30 carbon atoms or a radical of an organic acid, 000- CH1-o- 0Hcoo- E is oxygen or -NH-, 6H, (om), HO- COOH R gsiilclgldrogen or a saturated or unsaturated alkyl OOH HPCOOH r R is hydrogen or a carboxyl or sulphoxyl group, CXBHNWW 0113130001 OHHHCOCP, 918E130, R is hydrogen or a carboxyl group, and 6111133000 n is zero or a value from one to 100. d 10. A process according to claim 9 in which an I R is alkyl of eight to 22 carbon atoms, 25 R hydrogen 'CwHw 'CHZCOONa E i yg -CH2CH2COONB, CeHfCgHuy, *SO3H, PO Hg 01' R is hydrogen, -C H wherein q is eight to 18. R2 is a sulphoxyl group, 12. A process according to claim 8 wherein a meth- R is hydrogen or acarboxyl group, and ylol melamine or methylol urea is employed as comn is ero or a value from one to 1 0, v Pound II. A process according to claim 6 wherein in com- 13. A process as in claim 8 wherein the compound of pound formula (I) and the methylol compound are used in the R is weight ratio of 1:04 to 1:10.

14. A process according to claim 3 wherein the poo weight ratio of compound (a) to compound (c) is in the range of 30 z 7Q to 90:10.

-CO0H Hooo -COOH C60 (C 2) zNH C O CnHas

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3959230 *Jun 25, 1974May 25, 1976The Procter & Gamble CompanySoil release agents
US4702857 *Nov 22, 1985Oct 27, 1987The Procter & Gamble CompanyBlock polyesters and like compounds useful as soil release agents in detergent compositions
EP2742957A1 *Dec 6, 2013Jun 18, 2014Epitech Group S.r.l.Polyethylene glycol derivatives of palmitoylethanolamide and analogous acylethanolamides
Classifications
U.S. Classification427/212, 427/381, 427/394
International ClassificationC08G65/00, C08G65/28, D06M13/00, D06M15/37, D06M13/224, D06M15/53, D06M13/192
Cooperative ClassificationD06M13/224, D06M15/53, D06M13/192
European ClassificationD06M13/192, D06M15/53, D06M13/224