US2653140A - Textile finishing compositions - Google Patents

Description

7 formaldehyde condensation products.

Patented Sept. 22, 1953 2,653,140 .rsx'rms FINISHING COMPOSITION Owen Clement Wentworth Allenby, McMasterville, Quebec, Canada, and James Carroll Mac- Kenzie, Winchester, Mass., assignors to Canadian Industries Limited, Montreal,

Quebec.

Canada, a corporation of Canada No Drawing. Application November 19, 1952, Se-

rial No. 321,497. In Canada October 9, 1951 This invention relates to new textile finishing 'our copending application Serial No. 292,209 filed on June 6, 1952, now abandoned.

Durable compositions for the stiffening of cellulosic textile materials have heretofore been prepared by admixing starch with a thermosetting resin containing groups reactive to the hydroxyl groups of the starch and cellulose molecules. The cellulosic textile materials, when impregnated with the starch-resin mixture aid subsequently heated, show the effects of the stiffening composition for a considerable length of time due to the water-insolubilization or binding of the starch to the cellulosic material by means of the reactive thermosetting resin. Amongst the thermosetting resins which have heretofore been used, the most effective have been the formaldehyde condensation products such as the urea-formaldehyde or melamine- However, although these starch finishes are satisfactory from the point of view of durability, they all suffer from many disadvantages. For example, when the textile materials are treatedwith chlorine-containing bleaching agents, the starch finishes retain chlorine with resultant yellowing of the fabric and considerable loss in tensile strength upon ironing due to release of hydrogen chloride. Furthermore, fabrics treated with these starch finishes are all harsh to the hand. This is particularly true for starch finishes con taining polymerized dimethylol urea which are otherwise considerably laundry-fast even in a starch-resin ratio of 100-1.

It has now been found that if in addition to dimethylol urea, there is also incorporated with starch a water-soluble copolymer of an acid from the group consisting of acrylic'acid, methacrylic acid and crotonic acid, an amide selected from the group consisting of acrylamide, methacrylamide and crotonamide, and at least one monoethylenically unsaturated compound having the ethylenic group as sole reactive group, the fore going disadvantages are completely overcome. There are thus obtained new textile stiffening compositions which, despite their retention of chlorine when submitted to the action of chlorine-containing bleaching agents, do not affect 12 Claims. (01. 260-173) the colour or tensile strength of the fabrics upon ironing, and which, according to the kind of starch present therein, impart to the fabrics any type of hand desired, e. g. from a full warm hand to a sharp crisp hand, while possessing the same durability as the above-mentioned starch finishes of the prior art. It has also been found that these new compositions act as very effective pigment binders when used in the pigment printing of textile materials.

It is therefore an object of this invention to provide new textile finishing compositions.

Another object is to provide new durable textile finishing compositions.

A further object is to provide new durable compositions for the stiffening of textile materials.

A still further object is to prov de new durable compositions for the binding of pigments in the pigment printin of textile materials.

An additional object is to provide new durable compositions capable of imparting ,to textile materials a wide variety of hands.

Another object is to provide new durable textile finishing compositions which, after contact with chlorine-containing bleaching agents andupon ironing at high temperatures, do not afiect the colour or tensile strength of the finished textile materials.

other and additional objects will become apparent hereinafter. i

These objects are accomplished by the new compositions of this invention which broadly comprise starch in admixture with dimethylol urea and a water-soluble thermoplastic copolymer of an acid selected from the group consisting of acrylic acid, methacrylic acid and crotonic acid, an amide selected from the group consisting of acrylamide, methacrylamide and crotonamide, and at least one polymerizable monoethylenically unsaturated compound having the ethylenic group as sole reactive group. Preferred compositions suitable for the finishing of both heavy-weight and light-weight fabrics comprise an admixture of starch with dimethylol urea and a water-soluble thermoplastic copolymer of vinyl acetate, crotonic acid and crotonamide and, more particularly, an admixture of the latter ingredients in the following weight ratio: starch, 12.7; vinyl acetate-crotonic acidcrotonamide copolymer, 2.3; dimethylol urea, 1.

Fabrics impregnated with these compositions and heated at C. in an oven for five minutes show excellent ironability, increased body, resistance to discoloration on ironing after bleaching, and

of starch used, ranges from soft and full to crisp. If printed with pigments into which these compositions have been incorporated as hinders, the fabrics show good colour retention despite numerous intervening launderings.

As previously mentioned, the superior properties of the textile finishing compositions of this ingention over the compositions of the prior art are due to the incorporation of the water-soluble acid-amide copolymers into the mixtures of starch and dimethylol urea, and represent a totally unexpected result in the art of textile finishes embodying starch and urea-formaldehyde condensates.

The details and manner of practising the invention will be apparent by reference to the following specific examples, it being understood that these examples are merely illustrative embodiments of the'invention and that the scope of the invention is not limited thereto.

Example 1 A water-soluble thermoplastic copolymer containing 86% vinyl acetate, 8% crotonic acid and 6% crotonamide was prepared as follows:

215 parts of vinyl acetate were mixed with 20 parts of crotonic acid, 2.25 parts of crotonamide and parts of benzoyl peroxide and brought to refiux temperature for 5 minutes. 12.75 parts of crotonamide were then added to the refluxing mixture over a 35 minute period after which time the heating was continued until the temperature reached 105 C. i. e. for approximately 2 hours. The mixture was maintained at this temperature for 30 minutes, a total of 21:9 parts of hutanol being added in the course of the reaction to reduce the viscosity of the forming copolymers before completion of the copolymerization. The reaction mixture was cooled and mixed with aqueous ammonia so as to form a 20% aqueous solution of the water-soluble ammonium salt of the vinyl acetate-crotonic acid-crotonamide copolymer. This latter copolymer is not water-soluble in its free-acid form.

.A 5% solution of commercial corn starch was also prepared by stirring 16.2 parts of corn starch in 308 parts of water at 95 C. for five minutes.

The above starch solution was cooled to 50-60 C. and mixed with parts of the above copolymer solution and 4 parts of an 8% solution of dimethylol urea, thus providing a finish containing the starch, copolymer and dimethylol urea in the ratio of 12.7:2.3:0.25.

A x 20".piece of cotton muslin fabric weighing 6 oz. per sq. yard was thoroughly impregnated at 50-60 C. with the finish and sub- .4 piece of cotton muslin fabric, weighing 3.8 oz. per sq. yard, was thoroughly impregnated with the finish and subsequently air dried and uniformly ironed for 4 minutes at approximately 205 C. with a household iron. It was then given an initial wash to remove excess finish and then subjected to four successive launderings in a standard type rotary washer. The stiffening finish was thus found to be 65% laundry fast.

Example 3 To a 5% solution of commercial corn starch prepared as in Example 1, there were added 15 parts of the copolymer solution of Example 1, 4 parts of an 8% solution of dimethylol urea and 0.0032 part (1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. A 20" x 20" piece of cotton muslin fabric, weighing 3.8 oz. per sq. yard, was thoroughly impregnated with the finish and subsequently air dried and heated in an oven at 150 C. for 5 minutes. After an initial wash to remove excess finish and four successive launderings, the stiffening finish was found to be 67% laundry-fast.

Example 4 I methylol urea ratio of 12.7:23 :0.5, had a laundrysequently air dried and uniformly ironed for 2 A 5% solution of commercial corn starch was prepared as in Example 1 and mixed with 15 parts of the copolymer solution of Example 1, 4 parts of an 8% solution of dimethylol urea and 0.0016 part (0.5% by weight of dimethylol urea) of ammonium dihydrogen phosphate, A 20" x 20" fastness of Example 5 A 5% solution of commercial corn starch was prepared as in Example 1 and mixed with 15 parts of the copolymer solution of Example 1, 16 parts of an 8% solution of dimethylol urea and 0.0128 part (1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. There was thus obtained a stiffening finish having a starchzcopolymerzdimethylol urea ratio of 12362.3:1.

A ,20" x 20" piece of cotton muslin, weighing 2.2 oz. per sq. yard, was thoroughly impregnated with the finish and subsequently air dried and heated in an oven at 150 C. for 5 minutes. It was then given an initial wash to remove any ex-- cess finish and then subjected to twenty successive launderings in a standard-type rotary washer. The finish was thus found to be 88% laundry-fast after the fourth laundering, 73% after the ninth laundering and 50% after the twentieth laundering. The fabric still showed a full nice hand after the twentieth laundering.

Example 6 Three separate 20" x 20" pieces of cotton muslin, weighing 3.2 oz. per sq. yard, were impregnated with the stifi'ening finish of Example 5, air dried and then heated for 5 minute at 150 0., C., and 98 C. respectively. After an initial wash and t wenty repeated launderings, the laundry-fastness of the finish was found to be as follows:

Laundry-fastness Heating Temperature after 5th after 20th laundering laundering twentieth cycle. starch-urea/formaldehyde resin finish suffered Example 7 Two separate 20" x 20" pieces of cotton fabric, weighing 4.3 oz. per sq. yard, were impregnated, respectively, with 6.3% by weight of the fabric, of the stiffening finish of Example and 5.6% by weight of the fabric, of a stiffening finish containing starch and dimethylol urea in the ratio The fabrics were then submitted to very drastic hypochlorite bleaching retaining, respectively 0.046% and 0.060% chlorine. Upon ironing at 400 F. for 5 minutes, substantially no discolouration took place in the fabric treated with the finish of Example 5 whereas the other fabric showed considerable spotty yellowing. The loss in tenacity of the fabric finished with the starch dimethylol urea mixture .was about 44% as against 8% for the other fabric. The fabric treated with the starch-dimethylol urea mixture was harsh to the hand whereas the other fabric showed a nice full hand.

Example 8 phosphate. The finish thus obtained had a starch:copolymerzdimethylol urea ratio of 12.7 :2.3:1.

Various 8" x 18" pieces of cotton fabric were 7 then impregnated with the above finish and other similar pieces impregnated with a finish containing starch and a urea-formaldehyde resin in the ratio 4:1. The fabrics were then passed through rubber rolls to remove any excess finish, air dried and heated in an oven at 150 C. for 5 minutes. Some of the fabrics stiffened with the first finish were thensubjected to twenty successive launderings in a standard-type rotary washer in order to determine the laundry-fastness of the finish, while the remaining stiffened fabrics were subjected to twenty laundering and hypochlorite bleaching cycles in order to determine the postbleaching effects of both finishes upon ironing of the fabrics at approximately 205 C. with a household iron.

The starch-copolymer-dimethylolurea finish was thus found to be 97% laundry-fast after the fifth laundering, 85% laundry-fast after the tenth laundering, 78% laundry-fast after the fifteenth laundering and 73% laundry-fast after the twentieth laundering.

As regards post-bleaching effects upon ironing of the fabrics at approximately 205 C. with a household iron, substantially no discolouration took place in the fabrics treated with thestarchcopolymer-dimethylol urea finish even after the twentieth laundering and bleaching cycle wherethe fabrics treated with the starchurea/formaldehyde resin finish showed considerable spotty yellowing after the first cycle. The loss in tenacity of the fabrics finished with the starchecopolymer-dimethylol urea composition was the same as that of unfinished fabrics subjected to the same number of laundering and bleaching cycles, i. e.; about 50% after the The fabrics treated with the complete degradation after the twentieth cycle and holes appeared in the fabrics'as early as the third cycle.

Example 9 starch solutions was cooled to 50-60 C. and

mixed with 15 parts of the copolymer solutionof Example 1, 16 parts of an 8% aqueous solution of dimethylol urea and 0.0128 part (1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. There were thus obtained finishes having a starch:copolymerzdimethylol urea ratio of 12.7:2.3:1.

Six 8" x 18" pieces of cotton fabric were impregnated at 50 C. for one minute with the above finishes, passed through rubber rolls to remove any excess finish, and subsequently air dried and cured in an oven at 150 C. for five minutes. The stiffened pieces were then given a wash in a 0.25% castile soap solution containing 0.1% sodium carbonate for 5 minutes at 50 C. After three rinses in distilled water, the pieces were ironed dr at approximately 205 C. with a household iron, and redried in an oven at C. for 20 minutes. The following table illustrates the hand imparted to the stiffened cotton fabric by each finishas well as the amount of finish impregnated into the fabric, the latter being determined by weighing the pieces before impregnation and after the redrying period.

Example 10 A 5% solution of potato starch was prepared by adding 16.2 parts of potato starch to 308 parts of water and boiling the mixture for thirty minutes. The solution was then cooled to 55-60 C. and mixed with 11.6 parts of a 25.8% aqueous solution of the copolymer of Example 1, 16 parts of an 8% aqueous solution of dimethyl'ol urea and 0.0128 part (1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. To 80 parts of the resultant composition, there were then added 20 parts of a phthalocyanine green pigment paste and the mixture was stirred until a smooth paste was obtained. A similar paste was also prepared but using 10 parts of phthalocyam'ne pigment instead of 20 parts thereof.

Various 4 yard pieces of cotton, spun viscose rayon, acetate rayon, silk, nylon and polyethylene terephthalate fabric were then printed with each paste using a Mather and Platt laboratory printing machine, air dried and thereafter'baked in an oven at C. for 5 minutes. Two pieces of each fabric, i. e. one piece printed with the 20% paste and one piece printed with the 10% paste, were then tested for soaping fastncss by stirring continuously for 15 minutes in water con- 7 minutes at 50 C. in water containing 0.2% castlle .=oap and 0.1% sodium carbonate followed by Example 11 A water-soluble thermoplastic copolymer con-' taining 86% ethyl acrylate, 8% acrylic acid and 6% methacrylamide was prepared as follows:

215 parts of ethyl acrylate were mixed with 20 parts of acrylic acid, 15 parts of methacrylamide and 5 parts of benzoyl peroxide, and the mixture was heated at 75 C. for 45 minutes. A small amount of butanol' was'added at the start to curtail the vigorous reaction and reduce the viscosity of the forming copolymer. The temperature of the mixture was then allowed to raise slowly to 110 C. over a period of 55 minutes whereby the copolymerization was completed. The reaction mixture was thereafter cooled and mixed with aqueous ammonia so as to form a 25% aqueous solution of the water-soluble ammonium salt of the ethyl acrylate-acrylic acidmethacrylamide copolymer. This latter copolymer is not water-soluble in its free-acid form.

A 5% solution of potato starch was also prepared by stirring 16.2 parts of potato starch in 308 parts of water at 95 C. for thirty minutes. This solution was then cooled to 5060 C. and mixed with 12 parts of the above copolymer solution, 16 parts of an 8% solution of dimethylol urea and 0.0128 part (1% by weight of dimethylol urea) of ammonium dihydrogen phosphate. There was thus obtained a stiffening finish having a starch:copolymerzdimethylol urea ratio of l2.'7:2.3:1.

Two 20" x 20" pieces of cotton fabric were then impregnated with the above finish, air dried and heated in an oven at 150 C. for 5 minutes. After a preliminary wash to remove any excess finish one piece was subjected to five successive launderings in a standard-type rotary washer while the other piece was subjected to five consecutive laundering and hypochlorite bleaching cycles. The durability of the finish was determined by weighing the fabrics before impregna- ;ion and before and after each successive laundering and laundering-bleaching operation.

The results are shown in the following table in terms of percentage of finish impregnated in the fabrics.

Impregna- It-npregna" tion after Cycle tion after 1aundering laundering bleaching 4. 60 4. 55 4. 35 3. 95 4. 3. 4. l5 2. 85 4. 05 2. 2. s5 2. 0c

Neither fabric showed discoloration upon ironing at 400 F. for 1.5 minutes with a household iron.

Example 12 impregnaimpregna- Cycle tion after 322 223;

W-" bleaching Percent Percent Each fabric had a full, pleasant hand imparted thereto by the finish, and showed no discoloration upon ironing at 400 F. for 1.5 minutes with a household iron.

As illustrated by the foregoing examples, the durable finishes of this invention are readily and simply prepared as well as applied to textile materials and despite their retention of chlorine upon contact with hypochlorite bleaching agents, they do not produce any discolouration of the textile materials upon ironing thereof or any appreciable loss of tensile strength. Example 6 shows that it is preferable, from the point of view of durability, to bake the finishes at a temperature of at least C. The baking temperature can of course be raised over 150 C. with resultant shortening of the baking time. The presence of an acid baking catalyst does not appear to be essential for promoting the durability of the finishes as shown by Examples 1, 2 and 3.

Examples '7, 8 and 9 show the unexpected beneficial effects obtained by the incorporation of the water-soluble acid/amide copolymers into the known finishes containing starch and ureaformaldehyde condensation products. As regards the finishes of this invention when used for the pigment printing of textile materials, they are not deemed superior to prior pigment binding agents because of their bleach-stability since pigmented textile materials are not generally subjected to the action of bleaching agents. Their superiority over the pigment binders of the prior art is rather based on their initial water-solubility and hence ease of application, their heat convertibility to which they owe their durability, and also the wide variety of hands imparted thereby to the pigmented fabrics.

Although the examples show finishes containing acid/amide copolymers of only one composition, the composition of these copolymers may be varied without afiecting the durability and other beneficial properties of the finishes. The copolymers should, however, be soluble in water, viz. in their ammonium salt form, so as to be readily admixed with the aqueous solutions of starch and dimethylol urea. It is also possible to vary the composition of the finishes by changing the ratio of the various ingredients thereof. As above indicated, however, finishes having a starch: copolymer dimethylol urea ratio of 12.7:2.3:1, and more particularly a starchzvinyl acetate/crotonic acid/ crotonamide copolymendimethylol urea ratio of 12.7:2.3:1, have been found to be very suitable for both heavy-weight and light-weight textile materials.

Amongst the polymerizable monoethylenically unsaturated compounds having the ethylenic group as sole reactive group which can be used as components of the water-soluble copolymers of the finishes, there may be mentioned methyl acrylate. ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, vinyl acetate, vinyl propionate, styrene, vinyl naphthalene, etc.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it

' is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

Having thus described our invention what we claim is:

1. A textile finishing composition comprising as essential ingredients starch, dimethylol urea, and a water-soluble 'salt of a thermoplastic copolymer of an acid selected from the group .con sisting of acrylic acid, methacrylic acid and crotonic acid, an amide selected from the group consisting of acrylamide, methacrylamide and crotonamide, and at least one other polymerizable monoethylenically unsaturated compound selected from the group consisting of styrene, vinyl acetate and lower alkyl esters of acrylic acid and methacrylic acid.

2. A textile finishing composition comprising as essential ingredients starch, dimethylol urea, and a water-soluble salt of a thermoplastic copolymer of crotonic acid, crotonamide and vinyl acetate.

3. A textile finishing composition comprising as essential ingredients starch, dimethylol urea,

and a water-soluble salt of a thermoplastic copolymer of crotonic acid, crotonamide and vinyl acetate, in the following weight ratio: starch 12.7; dimethylol urea, 0.25-1.0; copolymer salt, 2.3.

4. A textile finishing composition comprising as essential ingredients starch, dimethylol urea, and a water-soluble salt of a thermoplastic copolymer of crotonic acid, crotonamide and vinyl acetate, in the following weight ratio: starch, 12.7; dimethylol urea, 1.0; copolymer salt, 2.3.

5. A textile finishing composition comprising as essential ingredients starch, dimethylol urea,

weight ratio: starch, 12.7; dimethylol urea, 1.0;

copolymer salt. 2.3.

7. A textile finishing composition consisting essentially of an aqueous solution of starch, dimethylol urea, and a water-soluble salt of a thermoplastic copolymer of an acid selected from. the group consisting of acrylic acid, methacrylic acid and crotonic acid, and amide selected from the group consisting of acrylamide,'methacrylamide and crotonamide, and at least one other polymerizable monoethylenically unsaturated compound selected from the group consisting of styrene, vinyl acetate and lower alkyl esters of acrylic acid and methacrylic acid.

8. A textile finishing composition consisting essentially of an aqueous solution of starch, d1- methylol urea, and a water-soluble salt of a thermoplastic copolymer of crotonic acid, crotonamide and vinyl acetate.

9. A textile finishing composition consisting essentially of an aqueous solution of starch, di-

11.'A textile finishing composition consisting essentially of an aqueous solution of starch, dimethylol urea, and a water-soluble salt of a triermoplastic copolymer containing 8 crotonic acid, 6% crotonamide and 86% vinyl acetate, in the following weight ratio: starch, 12.7; dimethylol urea, 1.0 copolymer salt, 2.3.

12. A textile finishing composition consisting essentially of an aqueous solution of starch, dimethylol urea, and the ammonium salt of a thermoplastic copolymer containing 8% crotonic acid,

6% crotonamide and 86% vinyl acetate, in the followingweight ratio: starch, 12.7; dimethylol urea, 1.0; copolymer salt, 2.3.

OWEN CLEMENT WENTWORTH ALLENBY. 'JAMES CARROLL MACKENZIE- References Cited in the tile of this patent Um'mn STATES PATENTS Name Date Acre et a1. June 12, 1945 Number

Claims (1)

1. A TEXTILE FINISHING COMPOSITION COMPRISING AS ESSENTIAL INGREDIENTS STARCH, DIMETHYLOL UREA, AND A WATER-SOLUBLE SALT OF A THERMOPLASTIC COPOLYMER OF AN ACID SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID, METHACRYLIC ACID AND CROTONIC ACID, AN AMIDE SELECTED FROM THE GROUP CONSISTING OF ACRYLAMIDE, METHACRYLAMIDE AND CROTONAMIDE, AND AT LEAST ONE OTHER POLYMERIZABLE MONOETHYLENICALLY UNSATURATED COMPOUND SELECTED FROM THE GROUP CONSISTING OF STYRENE, VINYL ACETATE AND LOWER ALKYL ESTERS OF ACRYLIC ACID AND METHACRYLIC ACID.