US3220869A

US3220869A - Process for improving textile fabrics

Info

Publication number: US3220869A
Authority: US
Inventors: Ruemens Wilhelm; Goetz Norbert; Zeidler Rolf; Tulo Herbert
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1959-03-13
Filing date: 1960-11-16
Publication date: 1965-11-30
Anticipated expiration: 1982-11-30
Also published as: DE1110606B; GB916698A; CH388244A; NL249327A; BE588503A; CH1180060A4; DE1128397B; SE310481B; NL128429C; CH407939A; CH231360A4; NL257973A; GB882743A

Description

United States Patent PRQCESS FGR IMPRQVING TEXTILE FABRME Wilhelm Ruemens, Norbert Goetz, Raff Zeitlier, and Herbert 'liulo, all of Ludwigshafen (Rhine), Germany,

assignors to Badische Anilin- & Soda-Fabrik Aktiengeseilschaft, Lndwigshafen (Rhine), Germany No Drawing. Filed Nov. 16, 1960, Ser. No. 69,540

Claims priority, application Germany Mar. 13, 1959,

B 52,466; Nov. 18, 1959, B 55,530 25 (Ilaims. (Cl. 11711) This application is a continuation-in-part of our copending application, Serial No. 14,208, filed March 11, 1960, now abandoned.

This invention relates to a textile finishing process which comprises impregnating cellulose fibers with a mixture of the reaction product of formaldehyde With an aminoplast-forming compound and a polymer.

It is known that the substances, as for example methylol compounds of aminoplast-forming compounds, usually employed for the creaseproofing of fabrics of cellulose, diminish the tensile strength of fabrics of native cellulose and diminish the abrasion resistance of fabrics of regenerated cellulose. In order to avoid this, it has been proposed to coemploy polymers or copolymers, as for example polyacrylic acid esters, in the creaseproofing. Fabrics treated in this way are however not stable to trichlorethylene, a compound used in dry cleaning processes. Moreover, it is necessary to accept the fact that the textile character is partly lost by too great stiffen- Furthermore plastic dispersions are known which are obtained by polymerization of mixtures of N-methylolamides of acrylic or methacrylic acid and other polymerizable compounds. These plastic dispersionshave already been proposed for the production of impregnations of textile fabrics.

We have now found that textile fabrics with a content of natural or regenerated cellulose of at least 25% by weight can be improved with especially good results by impregnating them with aqueous mixtures which contain (a) compounds which conventionally serve for creaseproofing, namely, reaction products of aminoplast-forming substances with formaldehyde and which contain in the molecule at least two nitrogen atoms and at least two methylol groups, which may be etherified, attached to nitrogen, and (b) copolymers derived from 1 to 25% by weight and especially advantageously 3 to 15% by weight of an N-methylolamide of acrylic acid or methacrylic acid and 99 to 75% by weight and especially advantageously 97 to 85% by weight of an ester formed from acrylic or methacrylic acid and a monohydric saturated aliphatic alcohol with 1 to 5 carbon atoms. The impregnated fabric is freed in the usual way from excess impregnating liquid until it contains 60 to 100% by weight of impregnating liquid with reference to the weight of untreated fabric (squeeze eifect 60 to 100%), preferably dried at 90 to 160 C. and then heated at a temperature above 100 C. and up to 200 C., preferably at 120 to 180 C.

Among the aminoplast-forming substanws of which the N-methylol compounds are to be used, compounds of the general formula:

3,220,800 Patented Nov. 30, 1965 in which R; and R are, for example, H, alkyl (for example, with 1 to 18 and especially 1 to 4 carbon atoms), C H or CN, or R and R together may be a divalent radical such as in which R may be H or an alkyl radical of the abovementioned kind, and X is in general :0, 8 or :NH, are especially suitable. Furthermore, there are suitable compounds of the general formula:

in which R.,, R and R may be H, alkyl, NH C H or OI-l and at least two of the radicals R to R must be -NH and also esters of carbamic acid with monohydric aliphatic alcohols, preferably with 1 to 4 carbon atoms, or amides or carboxylic acids with up to about 18 carbon atoms or diamides of dicarboxylic acids with up to about 10 carbon atoms.

The following are given as examples of compounds of the general Formula I which form aminoplasts with formaldehyde and of which the N-methylol compounds are of importance as creaseproofing agents: urea, diphenyl urea, methylurea, thiourea, dicyandiamide, guanidine, glyoxalmonoureine CO CO or triazinones R representing alkyl with 1 to 4 carbon atoms. Compounds of the general Formula II which are suitable for creaseproofing include melamine, methylmelamine and phenylmelamine. There are also suitable urethanes, polyurethanes, lactams, carboxylic acid amides, dicarboxylic acid diamides and polyamides. These aminoplast-forming substances are reacted in known manner with formaldehyde to form the corresponding Namethylol compounds. It is presupposed that at least two hydrogen atoms attached to nitrogen atoms in the molecule are replaced by the radical CH OH. There may also be used methylol compounds in which all hydrogen atoms attached to nitrogen and reacting with formaldehyde are replaced by methylol groups, and also all intermediate stages or their mixtures such as are often present in the reaction mixtures of aminoplast-forming compounds and formaldehyde. Suitable representatives include dimethylolurea, dimethylolurea dimethyl ether, dimethyldimethylolurea, dimethylolethyleneurea, dimethylolglyoxalmonoureine, tetramethylolglyoxaldiureine, dimethylolbutane-diol-diurethane, monoethyltrimethylolmelamine, hexamethylolmelamine, dimethylolethyltriazinone, dimethyl-isobutyltriazinone and dimethyloladipic acid diamide.

Etherified methylol compounds are also suitable. As the etherification agent there may serve in general monohydric saturated aliphatic alcohols, especially methanol, but alcohols of higher molecular weight of this group with up to about 4 carbon atoms may also be used, similarly the initial materials leading to the methylol compounds. It is preferable to add to the impregnating solutions, the acid hardening catalysts usual for the hardening of the methylol compounds. These are salts having an acid reaction in aqueous solution of metals of groups I, II and III (including NHJ) with acid residues of elements of groups VII, VI and V of the periodic system of elements, as for example the ammonium salts NH Cl, NH NO (NI- Q 80 sodium hydrogen sulfate NaHSO magnesium chloride MgCl zinc chloride ZnCl zinc nitrate Zn(NO zinc borofiuoride Zn(BF zinc silicofluoride ZnSiF and also carboxylic acids or other organic acids, such as tartaric acid, maleic acid, acetic acid or toluenesulfonic acid, and finally weak inorganic acids as, for example, boric acid. Mixtures of these compounds, especially the metal salts, with the acids are also suitable as hardening catalysts. It is possible by the use of much smaller amounts of hardenable methylol compounds than in the known finishing processes, to achieve equally good creaseproof effects. Tensile strength and abrasion resistance are considerably less impaired. The textile character remains unaffected. Moreover the finish obtained is stable to trichlorethylene.

The methylol compounds of the said aminoplast-forming compounds are in general used in concentrations between about 3 and 15% by weight of the textile finishing mixture in the usual way.

The copolymerization products used are prepared from monomer mixtures of 1 to 25% by weight of a compound of the general formula and 99 to 75% by weight of an ester derived from an acid and a monohydric saturated alcohol with 1 to carbon atoms, R and/or R being H or CH They are preferably used in aqueous dispersion in a concentration between about 1 and 20% by weight, especially between 4 and 12% by weight, with reference to the textile finishing mixture, the water content in the mixture being from 60 to 96% by weight.

Textile fabrics of pure natural or regenerated cellulose fibers and also mixtures of the same with other natural or synthetic fibers, such as wool, polyester fibers, poly acrylonitrile fibers and the like, may be used. Obviously, the softening, dressing and hydrophobing agents otherwise usual may be used as well. Pigment dyes or substantive dyes may also be added.

We have further found that mixtures of the above mentioned kind in which the copolymer has been prepared from 1 to 25% of an N-methylolamide of an acrylic acid and 99 to 75% of one or more copolymerizable compounds are eminently suitable for imparting to a fabric the properties required for the production of mechanical effects, the mechanical effects being produced by subjecting a fabric impregnated with said aqueous mixture, preferably after drying, to a mechanical treatment at an elevated temperature and heating the fabric thus treated again to a high temperature.

Mechanical treatment as used in the present specification is to be understood as including all measures which impart to textile fabrics an intentional change in shape. Such measures include, for example, embossing, pleating and schreinering. The fabrics are usually provided with the change in shape by treating them at an elevated temperature and under mechanical pressure one or more times with rollers whose surface is shaped or patterned as a relief. For pleating, pleating machines are used which bring the fabric into regular folds. The result of all these measures and the treatment according to this invention can be described as mechanical finishing.

It is very convenient to dry the fabric impregnated prior to the mechanical treatment, i.e., to free the fabric substantially from moisture. Drying may take place especially advantageously at temperatures of about 70 to C. It is favorable for the fabric thereafter to have a residual moisture content of about 8 to 14% or, in general, 6 to 14%. To apply the mechanical finish to the fabric, the latter may then for example be embossed, pleated or schreinered. For this purpose, temperatures of about 140 to 200 C. and the usual pressures, especially between 10 and 30 tons, are used. After the mechanical treatment, the fabric is again heated, for example in the usual way. The duration of the heating may be a few seconds up to about 10 minutes at temperatures between about 130 and 180 C. The finishing agent should be condensed on and with the fibers by the heating. Short heating periods are sufficient at high temperatures, but heating for longer periods is necessary at lower temperatures.

The mixtures which are preferred for impregnation prior to mechanical treatment are substantially the same as have been described above for the production of finishes to be applied without subsequent mechanical treatment. Accordingly, as copolymerizable monomers which may be copolymerized with acrylic acid or methacrylic acid N-methylolamides, there are above all suitable esters of acrylic or methacrylic acid, particularly esters of low molecular weight aliphatic alcohols, such as methanol, ethanol, butanols or pentanols. In addition to the said esters other monomers may be used, e.g., styrene, methylstyrene, vinyl chloride, vinyl ether, vinyl ester, or butadiene. As will be apparent from the working examples below, these additional monomers are generally to be used in a minor proportion with reference to the total weight of the copolymer (b). These specific additional monomers and other suitable monomers may be defined as monomers containing in the molecule a vinyl or an acrylic group as well as a radical representing halogen, a mononuclear ring of the benzene series, an esterified carboxylic group, an etherified hydroxy group, a group containing 1 to not more than 7 carbon atoms and, if desired, 1 or 2 oxygen atoms and/or 1 or 2 nitrogen atoms and/or 1 or 2 sulfur atoms. It is to be understood that the monomers specified are intended to illustrate, not to restrict our invention. The preferred methods for the preparation of mechanical finishes are the methods described for the preparation of finishes to be used without subsequent mechanical treatment.

The mechanical finishes obtained according to this invention are very durable mechanically and extremely re-.

istant to perspiration, laundering and dry cleaning. Even repeated washing at the boil with soap and soda or with the usual fine detergents does not affect the embossed effects.

The following examples will further illustrate this invention but the invention is not restricted to these examples. The parts specified in the examples are parts by weight.

Example 1 In an experiment A, a mercerized, bleached and dyed cotton poplin fabric is impregnated on a padding machine with a bath which contains in 1000 parts of water, 30 parts of dimethylolethyleneurca, 80 parts of a 40% aqueous dispersion of a copolymer of 95 parts of butyl acrylate and 5 parts of N-methylolacrylamide and 6 parts of magnesium chloride. The fabric is squeezed out, dried, heated for 5 minutes at 150 C. and if desired washed with one of the usual fine washing agents at 40 to 90 C. The fabric thus treated has a plesant handle and good resistance to creasing and abrasion, as may be seen from Table 1 below.

If the same fabric is impregnated in another experiment B with a bath which contains, in 1000 parts of water, 60 parts of dimethylolethyleneurea and 12 parts of magnesium chloride, but which does not contain any copolymer of butyl acrylate and methylolacrylamide, the tensile strength and abrasion resistance are considerably Examination of the abrasion resistance according to Repenning is described in the following literautre:

H. Sommer, Priifung von Textilien auf Widerstandsfahigkeit gegen Scheuerbeanspruchung, Klebzigs Textil- Zeitschrift, 1942, pages 264 to 276 and 446 to 451.

E. Wagner, Die Scheuerpriifung an Fasern, Garnen und Geweben, Technical Report 3 of the Wuppertal Textile Engineering School, also in Die Bekleidung, 1950, Nos. 2 and 4.

Example 2 In an experiment A, a mercerized, bleached and printed cotton poplin fabric is impregnated with a bath which contains, in 1000 parts of Water, 60 parts of a 50% aqueous solution of the dimethylol compound of glyoxalmonoureine, 100 parts of a 40% aqueous dispersion of a copolymer of 93 parts of butyl acrylate, 5 parts of N-methylolmethacrylamide and 2 parts of acrylic acid, 4 parts of polyglycol ether, parts of a 30% aqueous paste of a condensation product from 1 mol of stearic acid and 1 mol of triethanolamine and 8 parts of Zinc chloride. The fabric is squeezed oil, dried and heated for 5 minutes at 150 C. The handle of the fabric thus treated is soft, full and flowing. Resistance to creasing is good.

If in a similar experiment B a bath is used which contains, in 1000 parts of Water, 140 parts of a 50% aqueous solution of the dimethylol compound of glyoxalmonoureine and 14 parts of zinc chloride, the experimental values B shown in Table 2 are obtained.

TABLE 2 Crease angle Resistance to according to Tensile strength abrasion accord- DIN 53890 of the weft threads ing to Repenin kilograms ning, number of revolutions Warp Weft Fabric A 118 132 31.9 101 Fabric B 119 23. 4 72 Untreated 41 52 37. 1 94 Example 3 In an experiment A, a caustic-treated and dyed staple fiber fabric is impregnated with a bath which contains, in 1000 parts of water, 120 parts of a 70% aqueous solution of dimethyldimethylolurea, 60 parts of a 40% dispersion of a copolymer prepared with the use of potassium per sulfate as catalyst and the sodium salt of a paraflin sulfonic acid as emulsifier from about 5 parts of N-methylolacrylamide and 95 parts of butyl acrylate, and also 3 parts of ammonium nitrate. The fabric is then squeezed out and finally heated to C.

In a further experiment B, a bath is used which contains, in 1000 parts of water, 220 parts of a 70% aqueous solution of dimethyldimethylolurea and 4 parts of ammonium nitrate.

In an experiment A, caustic-treated and bleached cotton fabric is impregnated on a foulard with a bath which contains, in 1000 parts of water, 10 parts of dimethylolethyltriazinone, 30 parts of dimethylolglyoxalmonoureine, 100 parts of a 40% aqueous dispersion of a copolymer prepared with the use of potassium persulfate as catalyst and Turkey red oil as emulsifier from about 4 parts of N- methylolmethacrylamide, 1.2 parts of N-methylolacrylamide and 95 parts of butyl acrylate, and 12 parts of magnesium chloride. The fabric is then squeezed out, dried and heated at C. for 3 minutes.

When using a bath containing, in 1000 parts of Water, 10 parts of dimethylolethyltriazinone, 60 parts of dimethylolglyoxalmonoureine and 15 parts of magnesium chloride, the test data B are obtained.

In an experiment A, a caustic-treated, bleached and printed mixed fabric of 50% of cotton and 50% of staple fiber is impregnated on a foulard with a bath which contains, in 1000 parts of water, 60 parts of a 50% aqueous solution of dimethylolbutane-diol-diurethane, 70 parts of a 70% aqueous solution of dimethyldimethylolurea, 100 parts of a 40% aqueous dispersion of a copolymer prepared while using ammonium persulfate as catalyst and the sodium salt of a paraffin sulfonic acid as emulsifier from parts of methylolmethacrylamide, 40 parts of methyl methacrylate and 55 parts of butyl acrylate, 5 parts of polyglycol ether, 4 parts of stearylethyliminourea and 4 parts of ammonium nitrate. The fabric is squeezed out, dried and heated for 5 minutes at 150 C.

In a similar experiment B there is used instead a bath which contains, in 1000 parts of water, 120 parts of a 50% aqueous solution of dimethylolbutane-diol-diurethane, 140 parts of a 70% aqueous solution of dimethyldimethylolurea and 8 parts of ammonium nitrate, the test data B thus being obtained.

In an experiment A, a mercerized, bleached and dyed mixed fabric of 50% linen and 50% cotton is impregnated with a bath containing, in 1000 parts of water, 10 parts of tetramethylolacetone, 10 parts of dimethylolisobutyltriazinone, 20 parts of dimethylolethyleneurea, 90 parts of the copolymer dispersion used according to EX- ample 3 and 8 parts of zinc nitrate. The fabric is then squeezed out, dried and heated for 3 minutes at 160 C.

The values measured for fabric 13 are obtained by the use of 20 parts of tetramethylolacetone, 20 parts of dimethylolisobutyltriazinone, 40 parts of dimethylolethyleneurea and 15 parts of zinc nitrate in 1000 parts of water.

acopolymer dispersion as used in Example 4, 5 parts of a pigment paste of 30 parts of finely divided copper phthalocyanine and 5 parts of diammonium phosphate. The fabric is then squeezed out, dried and heated for 5 minutes at 150 C.

In an experiment 13, using a bath of 10 parts of monomethyltrimethylolmelamine, parts of dimethylolethyleneurea and 5 parts of diammonium phosphate in 1000 parts of water, test data B are obtained with the fabric thus treated.

In an experiment A, a non-mercerized bleached and dyed cotton fabric is impregnated on a foulard with an aqueous bath which contains, in 1000 parts, parts of a 70% aqueous crystal pulp of equal parts of monomethylolurea and dimethylolurea and 2 parts of monoammonium phosphate. The fabric is then squeezed out, dried and heated for 3 minutes at 140 C.

In a second experiment B, carried out in the same way, the aqueous bath contained, in 1000 parts, 150 parts of a 70% aqueous crystal pulp of equal parts of monomethylolurea and dimethylolurea and 3 parts of monoammonium phosphate.

In a third experiment C the same fabric is impregnated with an aqueous bath which contains, in 1000 parts, 100 parts of a 70% aqueous crystal pulp of equal parts of monomethylolurea and dimethylolurea and 2 parts of monoammoniumphosphate and also 50 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide.

From the following Table 8, which contains the crease recovery angle, tensile strength and tensile strength loss of the treated and, for comparison, of the untreated fabric, it may be seen that the fabric treated in experiment C has improved crease resistance while exhibiting similar tensile strength.

TABLE 8 Crease angle according Tensile strength of Loss of tensile strength to DIN 53890 in weft threads in kg.- in the weftdegrees Unwashed After Unwashed After a In percent After washing 0 washing 0 unwashed washing 0 105 31. 5 31. 5 26 23. 5 I 140 27. 0 27. 0 37. 5 34 Fabric C- 145 30. 5 30. 0 28 27 Untreated- 70 7O 42. 5 41. 5 0 0 TABLE 6 60 In the washing C, the fabric is washed for 30 minutes 0 Crease angle Resistance to at a temperature of 95 C. with a lye which contains 5 according to Tensile strength abrasion accordgrams of p and 2 grams of calcmed Soda P hter- D N 5 89 Oftheweftthreads l to Repen' The liquor ratio is 50:1.

in kilograms ning, number of revolutions Warp Weft 65 Example 9 g--. 38-2 2;; In an experiment A, a non-mercerized, bleached and mflj: 51 64 44:1 110 dyed cotton fabric is impregnated on a foulard with an aqueous bath which contains, in 1000 parts, 150 parts of Example 7 In an experiment A a bleached mixed fabric of 60% of cotton and 40% of polyterephthalic acid ethylene glycol ester is impregnated with a bath containing, in 1000 parts of water, 5 parts of monomethyltrimethylolmelamine, 30 parts of dimethylolethyleneurea, 150 parts of a 50% aqeuous solution of dimethylolglyoxalmonoureine, 5 parts of an aqueous 30% paste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolamine and 4 parts of diammonium phosphate. The fabric is then squeezed out, dried and heated for 3 minutes at C.

In an experiment B, the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 50 parts of a 50% aqueous solution of dimethylolglyoxalmonoureine, parts of a 30% aqueous plaste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolamine, 2 parts of diammonium phosphate and also 100 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide.

In a third experiment C carried out in analogous fashion the same fabric is impregnated with an aqueous bath TAB LE 10 which contains, in 1000 parts, 100 parts of a 50% aqueous solution of dimethylolglyoxalrnonoureine, 5 parts of Crease angle according to DIN 53890 in Loss of tensile Abrasion resista 30% q P of the condensatlsm producgfrom in the weft in degrees strength of the anceaceording to 1 mol of stearic acid and 2 mols of diethanolam ne, 3 {flt h W b g n s parts of diammonium phosphate and 50 parts of a 40% Aft g m percen O moms aqueous dispersion of a copolymer from 95 parts of butyl Washed Washes C acrylate and 5 parts of N-methylolmethacrylarnide.

While the crease recovery angle of the fabrics A, B Fabric 100 105 16 76 Fabric 13.... 135 140 35 66 and C is about the same, the tensile strength and abrasion 20 Fabric 115 120 16 80 resistance of the fabrics are considerably improved by the Fabric Dm 10 34 h h 1 f b 1 I d Fabric 140 145 20 75' treatment wit t e copo yrner o uty acry ate an Untreated 65 65 0 71 N-methlolmethacrylamide.

TABLE 9 Crease angle aecord- Tensile strength of Abrasion resistance ing to DIN 53890 the weft threads Loss of tensile according to in the weft in in kg. strength in percent Repenning-No.

degrees of revolutions Un- After 3 Un- After 3 Un- After 3 Un- After 3 washed washes C washed washes C washed washes C washed washes C 125 125 22. 0 23. 0 2s 64 65 125 115 25. 0 26. 0 19 18, 5 73 75 125 120 26. 5 27. 5 16 15. 5 83 83 untreated- 65 65 31. 5 32. 5 0 0 71 74 Example 10 Example 11 In an experiment A, a non-mercerized and bleached cotton fabric is impregnated with an aqueous bath which contains in 1000 parts, 50 parts of a 50% aqueous solution of dimethylolethyleneurea, 5 parts of a 30% aqueous paste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolamine and 2 parts of diammonium phosphate. Then the fabric is squeezed out, dried and heated for 3 minutes at 145 C.

In a second experiment B carried out analogously the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 150 parts of a 50% aqueous solution of dimethylolethyleneurea, 5 parts of a 30% aqueous paste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolamine and 4 parts of diammonium phosphate.

The same type of fabric, in an experiment C, is impregnated in the same way with an aqueous bath which contains, in 1000 parts, 50 parts of a 50% aqueous solution of dimethylolethyleneurea, 5 parts of a 30% aqueous paste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolarnine and 2 parts of diammonium phosphate, and also 50 parts of a aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide.

The same type of fabric is impregnated in the same way in an experiment D with an aqueous bath which contains, in 1000 parts, parts of a 50% solution of dimethylolurea, 5 parts of a 30% aqueous paste of the condensation product from 1 mol of stearic acid and 2 mols of diethanolamine and 2 parts of diammonium phosphate and 100 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-rnethylolmethacrylarnide.

In an experiment E, the same type of fabric is impregnated in the same way with a bath which contains, in 1000 parts, 100 parts of a 50% aqueous solution of dimethylolethyleneurea, 5 parts of a 30% aqueous paste of the condensation product from 1 mol of stearic acid and In an experiment A, a mercerized, bleached and dyed cotton poplin fabric is impregnated with an aqueous bath which contains, in 1000 parts, parts of a 50% aqueous solution of dimethylolglyoxalmonoureine and 4 parts of diammonium phosphate. The fabric is then squeezed out, dried and heated for 3 minutes at C. The fabric thus treated has good resistance to creasing and abrasion and exhibits only a slight loss of tensile strength.

In another experiment B carried out analogous-1y, an aqueous bath is used which in addition tothe substances used in experiment A contans 20 parts of a 40% aqueous dispersion of a copolymer from 45 parts of butadiene and 35 parts of acrylonitrile.

In a further experiment C, the bath contains, in addition to the compounds specified in experiement A in the concentration there specified, also 20 parts of a 55% aqueous dispersion of an addition copolymer of 75 parts of methyl acrylate, 24 parts of acrylic acid and 1 part of butenol.

In a further experiment D, a bath is used which contains, in addition to the compounds specified in experiment A in the concentrations there specified, also 20 parts of a 50% aqueous dispersion of vinyl propionate.

Finally, in an experiment E the same type of fabric is impregnated with a bath which contains, besides the compounds specified in experiment A in the concentrations there stated, also 20 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide.

The crease recovery angle, tensile strength and abrasion resistance of the fabrics A to E are shown in the following Table 11 together with the data for the untreated fabric. The use of the copolymer of butyl acrylate and N-methylolmethacrylamide according to the invention imparts a good crease resistance to the fabric E without too greatly diminishing its tensile strength.

TABLE 11 after a single wash C.]

Crease angle Tensile strength Loss of tensile Abrasion resistaccording to of the weft strength of the tance according DIN 53890 in threads in kg. weft threads in to Repenning the weft in degrees percent No. of revolutions U C U C U G U Fabric A 110 95 18. 18. 0 14 14. 5 215 200 Fabric B 130 115 18. 5 18. O 14 14. 5 220 220 Fabric 0 125 110 19.0 19.0 11. 5 9. 5 225 208 Fabric D. 130 100 18. 5 19. 5 14 7 212 207 Fabric E 130 125 19. 5 19. 5 9. 5 7 215 215 Untreated-.- 75 75 21. 5 21. 0 0 0 208 203 Example 12 ing in 1000 parts 50 parts of a 70% aqueous paste of In an experiment A, a staple fiber fabric is impregnated with an aqueous bath containing, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 150 parts of a 50% solution of tetramethylolacetylene diurea and 5 parts of ammonium nitrate. The fabric is then squeezed out, dried and heated for 4 minutes at 150 C. The fabric thus treated has a pleasant handle and good resistance to creasing as may be seen from the following Table 12.

In a further experiment B carried out analogously the same type of fabric is impregnated with a bath containing, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 100 parts of a 50% aqueous solution of tetramethylolacetylene diurea, 5 parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide and also 2 parts of an adduct from 6 to 7 mols of ethylene oxide to 1 mol of para-iso-octylphenol. The loss of abrasion resistance is substantially diminished and the wet crease angle somewhat further improved, while the tensile strength remains unchanged.

In a further experiment C carried out analogously the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 100 parts of a 50% aqueous solution of dimethylolglyoxalmonoureine and 5 parts of ammonium nitrate.

In another experiment D the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl e ther, 100 parts of a 50% solution of dimethylolglyoxalmonoureine, 5 parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 90 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide as Well as 2 parts of an adduct from 6 to 7 mols of ethylene oxide to 1 mol of para-iso-octylphenol. The loss in abrasion resistance is greatly diminished and the Wet crease recovery angle is improved.

In an experiment E the same type of fabric is impregnated with an aqueous bath containing, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 150 parts of a 50% aqueous solution of dimethylolethyleneurea and 5 parts of ammonium nitrate.

In a further experiment F the same type of fabric is impregnated with a bath containing, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 100 parst of a 50% solution of dimethylolethyleneurea, 5 parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide and also 2 parts of an adduct from 6 to 7 mols of ethylene oxide to 1 mol of para-iso-octylphenol. The loss of abrasion resistance is greatly diminished and the wet crease recovery angle improved.

In another experiment G carrid outanalogously the same type of fabric is impregnated with a bath containdimethylolurea dimethyl ether, 150 parts of a 50% solution of dimethylol-N-isobutyltriazinone and 5 parts of ammonium nitrate.

In an experiment H the same type of fabric is impregnated with a bath containing, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 100 parts of a 50% solution of dimethylol-N-isobutyltriazinone, 5 parts of ammonium nitrate and also 60 parts of a 40% aquous dispersion of a copolymer from parts of butyl acrylate and 5 parts of N-methylolmethacrylamide as well as 2 parts of an adduct from 6 to 7 mols of thylene oxide to 1 mol of para-iso-octylphenol. The loss in abrasion resistance is greatly diminished and the wet crease recovery angle improved.

In a further experiment I carried out analogously the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, 150 parts of a 50% solution of diemthylolbutane-diol-diurethane and 5 parts of ammonium nitrate.

The same type of fabric is impregnated in an experiment K with a bath which contains, in 1000 parts, 50 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, parts of a 50% aqueous solution of diemthyl ol-butant-diol-diurethane, 5 parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide, as Well as 2 parts of an adduct from 6 to 7 mols of ethylene oxide to 1 mol of paraiso-octylphenol. The loss of abrasion resistance is greatly diminished and the tensile strength and wet crease recovery angle improved.

In another experiment L carried out analogously the same type of fabric is impregnated with an aqueous bath containing, in 1000 parts, parts of a 70% aqueous solution of dimethylolurea, 60 parts of a 70% aqueous paste of dimethylolurea dimethyl ether, and 5 parts of ammonium nitrate.

In another experiment M the same type of fabric is impregnated with a bath which contains, in 1000 parts, 60 parts of a 70% aqueous solution of dimethylolurea, 60 parts of a 70% aqueous paste of diemthylolurea dimethyl ether, 5 parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide and 2 parts of an adduct from 6 to 7 mols of ethylene oxide to 1 mol of para-iso-octyl-phenol. The loss of abrasion resistance is greatly diminished and the Wet crease recovery angle slightly worsened.

In a further experiment N carried out analogously the same type of fabric is impregnated with an aqueous bath which contains, in 1000 parts, 120 parts of a 70% aqueous paste of equal parts of monomethylolurea and dimethylolurea, 60 parts of a 70% aqueous paste of diemthylolurea dimethyl ether and 5 parts of ammonium nitrate.

In an experiment 0 the same type of fabric is impregnated with a bath which contains, in 1000 parts, 60 parts of a 70% aqueous paste of equal parts of mono- 13 rnethylolurea and dimethylolurea, parts of ammonium nitrate and also 60 parts of a 40% aqueous dispersion of a copolymer from 95 parts of butyl acrylate and 5 parts of N-methylolmethacrylamide and also 2 parts of an adduct 14 The fabric thus finished has a pleasant handle. The mechanical finish is extremely resistant to laundering. The finish is not affected even by several washings at the boil.

from 6 to 7 mols of ethylene oxide to 1 mol of para-iso- 5 Example 14 octylphenol. The loss of abrasion resistance is diminished, the wet crease recovery angle somewhat improved and A f f fflbflc f 50% of cotton and 50% of rayon the dry crease recovery angle somewhat worsened. Staple 1S lmpregnated Wlth a minor Whlch contalns In In a further experiment P carried out analogously the 00 parts f Water 60 parts of dlmethylol ethylene urea same type of fabric is impregnated with an aqueous bath 10 or a dimethylol N-alkyltriazinone, 30 parts of dimethylolwhich contains, in 1000 parts, 50 parts of a 70% aqueous urea, 80 parts of a 40% aqueous dispersion of a copoly- Paste of dimethylohll'efl dimethyl ether, 0 parts of a 50% mer prepared according to Example 2 of German printed aqueous paste of equal parts of monqmethylolurea and specification No. 1,047,431 from 4 parts of N-methyloldlmethylolurea Parts of ammomum mtratemethacrylamide, 1.2 parts of N-methylolacrylamide and In a t g ii zlg hf fi l ogg rt 95 parts of butyl acrylate, 40 parts of a solution of a g gzgg g g l i i g h ih g y g copolymer derived from 60 parts of methacrylamide methyl ether, 80 parts of a 50% aqueous paste of equal and if g g iz gg sg j g parts of monomethylolurea and dimethylolurea, 5 parts P h 1 p d 6 t of ammonium nitrate and also 60 parts of a 40% aqueous 20 mo 0 a any am monoet ano aml an O dispersion of a copolymer of 95 parts of butyl acrylate 14 P of @thY1enB X,1de 5 y of n1tra te' and 5 Parts f N methy101methacry1amide as well 332 The impregnated fabric is dr1ed at 120 C. unt1l the residparts f an dd f 6 to 7 l f ethylene Oxide to 1 ual moisture amounts to 11 to 13%. The fabnc 1s then mol of para-iso-octylphenol. The loss of abrasion resisttreated on a hr iner Calender at 190 C. and under a ance is diminished and the wet crease recovery angle impressure of 25 metric tons and finally heated for 5 minproved. utes at 155 C.

In the following Table 12, the dry and wet crease angles The schreiner effect obtained is extremely resistant to are determined in the weft according to DIN 53890, the i ti ,1 d -i d d l i tensile strength 1s determined in l 1lograms in the weft threads, the abrasion resistance is determined in numbers Example 15 of revolutions according to Repenning, and the loss of abrasion resistance is given as a percentage. U stands for A fibnc conslsiuig of rayon i the rap rayon unwashed fabric, 18 and 5B designate a fabric which has staple in the weft 1s nnpregnated w1th a hquor wh1ch conbeen given 1 or 5 washes B, and 1C and represent tams m 1000 Parts of .water parts of i a f b i which has been given 1 or 5 Washes C. 35 oxal monourelne or dlmethylol butane-dlol diurethane,

In a Washing h f b i i Washed f 30 minutes 20 parts of dimethylol melamine, 70 parts of a 40% aqueat a temperature of C. with a lye which contains 5 011S dispersion of a COPOIYITIET derived from 93 Parts of grams of soap and 2 grams of calcined soda per liter, butyl acrylate, 5 Parts of N-methylol methacl'ylamlde and the liquor ratio is 50:1. 2 parts of acrylic acid, 15 parts of polyglycol ether, 2

TABLE 12 Dry crease angle Wet crease angle Loss of Fabric Tensile Abrasion abrasion U 1B 5B 10 56 U 1B 5B 10 50 strength resistance resistance 125 125 130 130 125 120 115 130 125 33.5 45 52.5 135 120 125 130 140 150 155 155 150 33 25.5 140 130 135 120 125 120 120 130 130 29.5 45 52.5 135 120 125 130 140 150 155 155 150 33 70 25.5 140 135 140 140 120 125 115 125 135 31.5 45 52.5 135 130 125 120 150 150 155 150 155 33.5 21 140 130 135 130 115 120 120 35.5 50 47.5 115 120 120 155 145 145 145 150 37 so 15 115 115 115 105 135 145 140 150 150 29.5 55 42 120 125 120 100 155 150 150 155 150 39 95 0 145 140 135 125 120 130 130 35.5 45 52.5 135 130 125 105 150 150 150 150 155 37 so 15 150 125 115 115 130 140 140 35.5 50 47.5 140 120 125 115 145 145 155 145 35 75 21 145 130 130 125 120 130 125 130 130 33 40 53 Q 135 130 130 115 150 150 155 150 35 7 25.5 Untreated 90 110 105 90 110 85 90 95 35 95 32.5 95 0 Example 13 60 parts of polyvinyl chloride and 5 parts of ammonium A rayon staple fiber fabric, which may have been dyed chlor de. The lmpregnated fabric 1s dr1ed at 90 C. to or printed is impregnated with a bath containing in 1000 a residual mo1sture content of 8 to 16%, then pleated at parts of water 75 parts of tetramethyloy glyoxal diureine, i gi g i i hiated f 5 30 parts of diemthylolurea dimethyl ether, 60 parts of a 9" es a e ea 6 e 15 reme y re- 40% aqueous dispersion of a copolymer derived from 5 65 SStant to lautldenng is scarcely Impaired even by parts of N-methylolmethacrylarnide and 95 parts of butyl repute; z i h k b1 t t acrylate (German printed specification No. 1,047,431), 10 Fun 2m; a Ions E c i refmar i i parts of a copolymer derived from 50 parts of acrylamide mechamfia ms can 6 ma 6 p POIH e o ow1ng and 50 parts of methacrylamide 2 Parts of a reaction agents g1ven by way of example. Each formulanon w1ll 70 contain one agent I, one agent II, one dispersing agent product of iso-octylphenol with ethylene oxide and 5 parts of ammonium nitrate. The fabric thus impregnated is dried at 100 C. until it has a residual moisture content of about 12%. It is then embossed at 180 C. by applying a pressure of about 15 metric tons, and finally heated for 5 minutes at C.

III serving for the stabilization of the impregnating liquor, and one agent IV which is the catalyst necessary for hardening the impregnating agent. To prepare the impregnating liquor, the agents are added in the given amounts or range of amounts to 1000 parts of water.

1 Agent I.40 to 80 parts of:

tetramethylol glyoxal diureine, or dimethylol glyoxal monoureine, or dimethylol butane-diol diurethane, or

a dimethylol-N-alkyl-substituted triaz'one, of dimethylol ethylene urea, or

trimethylol melamine, or

hexamethylol melamine.

Agent Ila.60 parts of a 40% aqueous dispersion of a copolymer derived from:

Agent IIb.60 parts of a 40% aqueous dispersion of a copolymer derived from:

30 to 60 parts of styrene, 70 to 40 parts of butyl acrylate or methyl-pentyl acrylate and 5 to 15 parts of N-rnethylolmethacrylamide.

Dispersion agent IlI.-2 to 5 parts of a reaction product of iso-octylphenol or a fatty acid monoethanol amide with ethylene oxide.

Agent I V.4 to 7 parts of ammonium nitrate, ammo- I nium chloride, ammonium sulfate, monoammonium phosphate or diammonium phosphate, or

10 to parts of zinc nitrate, or 15 to parts of magnesium chloride.

Dyed or printed cotton is impregnated with the liquor, dried at 70 to 100 C. to a residual moisture content of 10 to 12% embossed (or schreinered) at 170 to 210 C. and a pressure of about 10 to metric tons and heated for 5 minutes at 150 to 160 C. or for 2 minutes at 170 C.

The mechanical finish thus obtained is extremely resistant to laundering and is not impaired even by several washings at the boil. The fabric has a pleasant flowing handle when an agent Ha has been used, and a full firm handle when an agent IIb has been used. Any variant of the handle can be obtained by mixing an agent IIa with an agent III), the handle depending on the mixing ratio.

Instead of a single agent I, a mixture of two or more of the agents I may be used. The same is true of agent IIa.

For finishing staple fiber fabrics and mixed fabrics, for example of rayon and rayon staple or rayon staple and cotton, it is especially convenient to use mixtures of (a) an agent suitable for creaseproofing which upon condensation at least mainly condenses with itself and crosslinks and (b) an agent suitable for creaseproofing which during condensation crosslinks with the fiber and with itself. Therefore, besides the above-mentioned agents, for example, to 70 parts of dimethylol urea dimethyl ether or an ether of trior hexamethylol melamine (for example, a methyl, ethyl or glycol ether) are added to the impregnating liquor. Mixtures of ethers may also be used.

In the process according to this invention it is not necessary for the mechanical treatment to be carried out immediately following the drying or impregnation. The impregnated fabric may also be allowed to lie for hours or days and only then subjected to the mechanical treatment.

What we claim is:

1. A process for improving a textile fabric which contains at least 25% by weight of cellulose fibers said process comprising treating said textile fabric with an aqueous liquor which contains:

(a) a reaction product of an aminoplast-forming substance with formaldehyde which contains in the molecule at least two nitrogen atoms and connected to nitrogen, at least two radicals selected from the group consisting of methylol groups and etherified methylol groups, and

(b) a copolymer formed from about 1 to 25% by weight of a compound of the general formula H2C=CC O-NCH2OH in which R stands for a radical selected from the group consisting of -H and -CH and about 99 to by weight of an ester formed from an acid H2C=CCOOH in which R stands for a radical selected from the group consisting of H and -CH and a monohydric saturated aliphatic alcohol with 1 to 5 carbon atoms, freeing the impregnated fabric from excessive impregnation liquid, and then heating the impregnated fabric to above 100 C. up to about 200 C. for polycondensation of the aminoplast. 2. A process as claimed in claim 1 wherein the copolymer (b) used consists of 3 to 15% by weight of a compound of the general formula in which R stands for a radical selected from the group consisting of H and CH and 97 to 85% by weight of an ester formed from an acid in which R stands for a radical selected from the group consisting of --H and CH and a monohydric saturated aliphatic alcohol with 1 to 5 carbon atoms.

3. A process as claimed in claim 1 wherein after drying the product is heated to a temperature between about and 180 C. for polycondensation of the aminoplast.

4. A process as claimed in claim 1 wherein the component (a) is contained in the impregnation liquid in a concentration between 3 and 15% by weight.

5. A process as claimed in claim 1 wherein the component (b) is contained in the impregnation liquid in a concentration between 1 and 20% by weight.

6. A process as claimed in claim 1 wherein the component (b) is contained in the impregnation liquid in a concentration between 4 and 12% by Weight.

7. A process as claimed in claim 1 wherein the impregnated fabric is freed from excess of impregnation liquid until it contains 60 to 100% by weight of impregnation liquid with reference to the weight of the untreated fabric.

8. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolethyleneurea and as component (b) a copolymer from butyl acrylate and N-methylolacrylamide.

9. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolglyoxalmonoureine and as component (b) a copolymer from butyl acrylate, N-methylolmethacrylamide and acrylic acid.

10. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethyldimethylolurea and as component (b) a copolymer from butyl acrylate and N-methylolmethacrylamide.

11. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolethyltriazinone and dimethylolglyoxalmonoureine and as component (b) a copolymer from butyl acrylate, N-methylolacrylamide and N-methylolmethacrylamide.

12. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylol-butane-diol-diurethan and dimethyldimethylolurea and as component (b) a copolymer from methyl methacrylate, butyl acrylate and N-methylolmethacrylamide.

13. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolisobutyltriazinone and dimethylolethyleneurea and as component (b) a copolymer from butyl acrylate and N-methylolacrylamide.

14. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolethyleneurea and monomethyltrimethylolmelamine and as component (b) a copolymer from butyl acrylate, N-methylolacrylamide and N-methylolmethacrylamide.

15. A process as claimed in claim 1 wherein the liquor contains as component (a) monomethylolurea and dimethylolurea and as component (b) a copolymer from propyl acrylate and N-methylolmethacrylamide.

16. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolurea dimethyl ether and tetrametylolacetylene diurea and as component (b) a copolymer from butyl acrylate and N-methylolmet'hacrylamide.

17. A process as claimed in claim 1 wherein the liquor contains as component (a) dirnethylolurea dimethyl ether and dimethylol-N-isobutyltriazinone and as component (b) a copolymer fro mbutyl acrylate and N-methylolmethacrylarnide.

18. A process as claimed in claim 1 wherein the liquor contains as component (a) dimethylolurea dimethyl ether and dimethylolbutane-diol-diurethan and as component (b) a copolymer from butyl acrylate and N-methylolacrylamide.

19. A process as claimed in claim 1 wherein the liquor also contains an acid-reacting hardening catalyst selected from the class consisting of acid-reacting salts and weak acids.

20. A textile material which has been improved by the process claimed in claim 1.

21. A composition for improving a textile fabric containing at least 25% by weight of cellulose fibers said composition consisting essentially of an aqueous dispersion of (a) a reaction product of an aminoplast-forming substance with formaldehyde which contains in the molecule at least two nitrogen atoms and, attached to nitrogen, at least two radicals selected from the group consisting of methylol groups and etherified methylol groups and (b) a copolymer formed from about 1 to 25% by weight of a compound of the general formula in which R stands for a radical selected from the group consisting of H and CH and about 99 to 75% by weight of an ester formed from an acid in which R stands for a radical selected from the group consisting of H and -CH and a monohydric saturated aliphatic alcohol with 1 to 5 carbon atoms, said composition containing from 3 to 15% by weight of said reaction product with reference to the total weight of said composition and from 1 to 20% by weight of said copolymer with reference to the total weight of said composition.

22. A composition as claimed in claim 21 wherein said copolymer (b) contains a minor proportion of at least one copolymerizable monomer selected from the group consisting of acrylic acid, styrene, methylstyrene, vinyl chloride, vinyl ether, vinyl ester and butadiene.

23. A composition as claimed in claim 22 wherein said component (b) is a copolymer of N-methylolmethacrylamide, acrylic acid and butyl acrylate.

24. A composition as claimed in claim 22 wherein said component (b) is a copolymer of N-methylolmethacrylamide, styrene and butyl acrylate.

25. A process for improving a textile fabric which contains at least 25 by weight of cellulose fibers said process comprising treating said textile fabric with an aqueous liquor which contains (a) a reaction product of an aminoplast-forming substance with formaldehyde which contains in the molecule at least two nitrogen atoms and connected to nitrogen, at least two radicals selected from the group consisting of methylol groups and etherified methylol groups, and (b) a copolymer from 1 to 25% by weight of a compound of the general formula H2C=(IJO O1TIOH2OH' in which R stands for a radical selected from the group consisting of H and -CH and 99 to by weight of an ester formed from an acid in which R stands for a radical selected from the group consisting of H and CH and a monohydric saturated aliphatic alcohol with 1 to 5 carbon atoms, freeing the impregnated fabric from excessive impregnation liquid, changing the shape of said fabric by mechanical deformation, and heating the impregnated fabric to a temperature between and C.

References Cited by the Examiner UNITED STATES PATENTS 2,536,050 1/1951 Fluck 117139.4 2,819,179 1/1958 Barnard et a1. 117139.5 2,864,093 12/1958 Summer et a1. 117140 X 2,876,062 3/1959 Torke et a1. 117139.4 X 2,950,553 8/1960 HurWitZ 117 139.4 X 2,974,432 3/1961 Waxnock et al. 117139.4 X 2,976,167 3/1961 Maeder et al. 11733 3,037,963 6/1962 Christensen 260-452 WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner.

Claims

1. A PROCESS FOR IMPROVING A TEXTILE FABRIC WHICH CONTAINS AT LEAST 25% BY WEIGHT OF CELLULOSE FIBERS SAID PROCCESS COMPRISING TREATING SAID TEXTILE FABRIC WITH AN AQUEOUS LIQUOR WHICH CONTAINS: (A) A REACTION PRODUCT OF AN AMINOPLAST-FORMING SUBSTANCE WITH FORMALDEHYLE WHICH CONTAINS IN THE MOLECULE AT LEAST TWO NITROGEN ATOMS AND CONNECTED TO NITROGEN, AT LEAST TWO RADICALS SELECTED FROM THE GROUP CONSISTING OF METHYLOL GROUPS AND ETHERIFIED METHYLOL GROUPS, AND (B) A COPOLYMER FORMED FROM ABOUT 1 TO 25% BY WEIGHT OF A COMPOUND OF THE GENERAL FORMULA