US3666400A - Sizing of yarns and fibers with combinations of polymers and crosslinking agents - Google Patents

Abstract

THIS INVENTION RELATES TO A PROCESS FOR PRODUCING A DURABLE-PRESS FABRIC HAVING A SUPERIOR ABRASION RESISTANCE. CELLULOSIC TEXTILE YARNS ARE SIZED WITH A COMBINATION OF A PERMANENT POLYMER, A TEMPORARY POLYMER AND A CROSSLINKING AGENT PRIOR TO WEAVING. THE PERMANENT POLYMER INCLUDES POLYURETHANES, POLYACRYLATES, BUTADIENE-STYRENE COPOLYMERS, BUTADIENE-ACRYLONITRILE COPOLYMERS, AND ETHYLENE-VINYLACETATE COPOLYMERS. A TEMPORARY POLYMER IS POLYVINYL ALCOHOL. CROSSLINKING AGENTS INCLUDE DIMETHYLOL DIHYDROXY-ETHYLENUREA (DMDHEU), DIMETHYLOL METHOXYETHYLACARBAMATE, METHYLOL MELAMINE, AND DIMETHYLOL PROPYLENEUREA.

Description

United States Patent Ofice 3,666,400 Patented May 30, 1972 SIZING OF YARNS AND FIBERS WITH COMBINA- TIONS OF POLYMERS AND CROSSLINKING AGENTS John T. Lofton and Robert J. Harper, In, Metairie, and Eugene J. Blanchard, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Continuation-impart of application Ser. No. 756,323, Aug. 29, 1968. This application Mar. 10, 1970, Ser. No. 18,292

Int. Cl. D06m 13/52, 15/70 US. Cl. 8115.6 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a process for producing a durable-press fabric having a superior abrasion resistance. Cellulosic textile yarns are sized with a combination of a permanent polymer, a temporary polymer and a crosslinking agent prior to weaving. The permanent polymer includes polyurethanes, polyacrylates, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, and ethylene-vinylacetate copolymers. A temporary polymer is polyvinyl alcohol. Crosslinking agents include dimethylol dihydroxy-ethylenurea (DMDHEU), dimethylol methoX- yethylcarbamate, methylol melamine, and dimethylol propyleneurea.

This is a continuation-in-part of Ser. No. 756,323 filed Aug. 29', 1968, now abandoned.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

The primary object of this invention is to provide a method for producing durable-press fabrics with superior abrasion resistance. In this method, textile fibers and crosslinking agents are sized with a combination of permanent polymer additive, temporary polymer agent and crosslinking agent prior to weaving. The polymer additive employed is one which improves the wrinkle recovery or abrasion resistance when applied to woven fabric. By application of the polymer additive to the yarn, prior to weaving, the polymer additive serves the dual purpose of acting as a weaving size and improving the wrinkle recovery of the finished fabric. The use of a crosslinking agent in conjunction with the temporary sizing agent provides a method by which the temporary agent becomes permanently attached to the fabric. By use of the crosslinking agent in the size, a less than normal amount of crosslinking agent can be utilized in finishing the fabric subsequent to weaving. This procedure provides a method of producing fabrics with smooth drying appearance and improved abrasion resistance.

Heretofore sizing mixtures have been designed to be temporary and are removed by desizing operations immediately after weaving. Permanent polymers are then applied to the fabric. Polymers applied to the fabric tend to stiffen the fabric and at times lead to undesirable yarn binding. This higher degree of stiffness is detrimental from the viewpoint of the esthetics of the fabric to the wearer as well as abrasion resistance in the garment manufactured from such fabrics.

By the process of this invention, polymers and crosslinking agents can be applied to yarns in the normal manner that starch size is applied. The types of polymers which have been successfully utilized have been polyurethanes, polyacrylates, and butadiene-styrene copolymers. The types of temporary sizing agents used in this research include polyvinyl alcohol and carboxymethyl cellulose. The types of crosslinking agents used include dimethylol dihydroxyethyleneurea and methylol melamines. The warp yarn is passed through the emulsion, squeezed, and dried and cured in some cases. The resulting warp beam is then loomed and woven into a fabric. The woven fabric can be scoured, bleached, and dyed. Durable-press crosslinking agents and other finishing auxiliaries are then padded onto the fabric and dried.

The advantages of using permanent polymer sizing are many. Polymers can be applied to the yarns in the normal manner that starch size is applied at the slasher. This. eliminates the desizing procedure normally encountered in the application of a temporary sizing. Efficiency in weaving is equal to or better than regular starch size. It is also possible to vary the conditions of sizing. For example, you can use permanent sizing in warp and filling, permanent sizing in the warp direction only, or a combination of permanent and temporary sizing. Another advantage of applying the permanent polymer to the yarn and then weaving the fabric in contrast to application of the polymer to the woven fabric is that the resultant yarn treated fabrics are softer than the fabrics treated with the same polymer add-on. This reduced stifiness improves edge abrasion resistance. Durable-press fabrics, which have polymers only in the warp direction, do not have the exceedingly low crease sharpness values exhibited by fabrics which have been treated with the same polymers as fabric treatments.

Yarns can be sized with a combination of temporary and permanent sizing agents. This type formulation has cost advantages over the use of permanent sizing agents only. Under certain conditions temporary agents such as PVA/CMC can be crosslinked to produce fabrics with excellent durable-press performances and a substantial improvement in fabric strength properties.

In this method, textile fibers/yarns are sized with permanent polymers and combinations of these ingredients with crosslinking resins. This method produces good durable-press fabrics with low resin concentrations; thus improving physical properties with cost saving finishes. Directional application of polymer and crosslinking agents can be used to control physical properties, wrinkle recovery, and abrasion resistance of a preferred yarn direction in the finished fabric.

Other variations to this same basic treatment are also possible. A brief description and explanation of these variations will be given.

First, it is possible to prepare fabrics from polymer sized warp and filling yarns, and it is also possible to prepare fabrics from yarns treated with a combination of polymers and crosslinking agents. If the same polymer and crosslinking agent are used for both the warp and filling treatment, the resultant fabric is softer than the fabric treated with the same polymer. The yarn-treated fabrics then can be raised to durable-press performance with a lower level of crosslinking treatment or an equivalent level of crosslinking treatment. The yarn-treated fabric is softer and has improved abrasion resistance.

In a second variation, yarns were sized with one polymer in the warp direction and a second polymer in the filling direction. No such fabric can be produced from a fabric treatment and the types of polymers used for the warp and filling treatments can be used to control or modify final properties such as breaking strength, crease sharpness, fabric stiffness and other properties.

A special variation of sized warp and filling yarn fabrics can be employed to achieve certain unique fabric properties. Thus, it was found that heavyweight fabrics prepared from warp and filling polymer-treated yarns (particularly 2-ply yarns) can be used to produce a fabric which has good wash-wear appearance with no further treatment other than application of a softener. Cuffs prepared from such fabrics showed good wash-wear appearance and crease sharpness through 30 launderings. The

4 The following examples illustrate but do not limit the scope of this invention. All percentages are by weight.

EXAMPLE 1 1% of a zinc nitrate based solution. Loom run.

smooth drying and crease sharpness of such fabrics arise An twill fabric was woven from Warp and fining from the heat-set treatment of the polymer. Such fabrics, yams sized with 2% PVA and 2 7% lowmmperamre therefore, have the special advantage of no odor release in DMDHEU and 1% of a zinc I'fitrate base catalyst the cutting room. A second advantage would be that the Warp yams were cumd on Slasher dry cans; fas ia:instantiate?asserts; g t a ment with these heavyweight goods is that the warp and ig gi 22 g ig gs gfi? d 2 gigigggf ggg g gg m fgg g ggz g g $23: 1.4% of a zinc nitrate base catalyst. The second salmpql e into trousers and then heat set to produce crease and 2?; if i giggg gig gSf i zg g ggg 123 6: as: 32 3213223.?i5223i,1223.333.i ttif fififfii? g of dehyde odor in garment plants) with the further ad- S$2 fiz ggi i i i gfigggg fg g; gf g gi zz iifi i fi ggigi g ggggr appearance and ennitrate based catalyst. All three fabrics had comparable Another general area of variation in these yarn-treated g a gg i 2?? the 1st and 20th Wash fabrics would be to use a combination of permanent and eye S are 5 Wm m a e temporary (standard) size in these yarn treatments. The EXAMPLE 2 temporary size may then be removed leaving the desired level of permanent size. This approach has the advantage In another experiment the above fabric was woven of economy since the polymers used in permanent sizing from warp yarns treated with 2.5% solids polyurethane, generally are more expensive than temporary size agents. 3% PVA, 2.7% solution DMDHEU and 1% of a zinc A further variation of the use of permanent and temporary nitrate based catalyst, and an untreated filling. One porsizing was observed when such fabric Was crosslinkcd tion of the fabric was desized, scoured, and treated with without any intermediate desizing operation. In several a 4% solution of DMDHEU. The other portion was cases where both the warp and filling yarns were teste cured on a tenter frame at 320 F., desized, scoured, and with combinations of permanent and temporary sizes and treated with a 1.8% solution DMDHEU and 0.5% of a crosslinked Without desizing, fabrics were obtained with zinc nitrate base catalyst. Results in Table II. 300 WRA and exceedingly high retention of breaking strength. For example, breaking strength retention was XA 3 96% in the warp direction and 85% in the filling direcp tion. By contrast a conventional treatment on the non- In another extferlment, a fabric Was woven from p polymer-treated (control) fabric had 39% retention in Y treated with 4 {nethylol melamlfle d 3% the warp direction and 32% retention in the filling direc- PVA and 0.5% of a 11116 filtrate base catalysi- A Partlal tion cure was dgne ondtiheistealrlnfar; as:4 513113 gagric avalsqther 40 scoured an repa e wi 0 an 0 o ggg a g fg g ggz 2122113238 3 32 2233335333 a zirrdc nitrate base catalyst. The fabric was then dried and tem orar size and crosslinkin a ents in the yarn treatcure y men is. Tiivo variables are pos sibli in this case. In one fi Second, fabnc was similarly i fixcept the w variation, a partial cure is applied to yarns so that only a z ig POPaCFYIate addmon to 3% a part of temporary size is removed in the desizing operaan 0 me y 0 me l tion. In the second case, a full cure is applied to yarns A was also i m Winch the crosslinkmg agent prior to desizing. By this latter method, most of the was apphed q z and scoured fabnc only The temporary size is converted to a permanent polymer additr.eatm.em conslste 0 63% DMD HEU and 25% of a five on the fabric zinc nitrate base catalyst.

Results are shown in Table III. Permanent polymers which can be used by the process of this invention include polyurethanes, polyacrylates, EXAMPLE 4 butadiene-styrene copolymeri, butadiene-acrylonitrile co- Polymers, and etbylene'vinylacetbte PP in the In another experiment, the fabric was woven from warp Tange 0f ab11t4% to 20% y Welghtwith filllng Yarns, yarn treated with 8% polyacrylate, 3% PVA, 1.4% Polymers can be used in the range from 1% W 20% and DMDHEU and 0.5% of a zinc nitrate base catalyst. The can a so include Silicones, Polyethylene and P YP PY filling yarns were untreated. After the fabric was woven, cfosslinking agents inclbde dimethylol dihydroxy' it was given a full cure. The fabric was then scoured and ethyleneurea dimethylol methoxyethylcarpadded with 3.6% DMDHEU and 1.5% of a zinc nitrate bamate, and methylol melamine propyleneurea in the b catalyst Th fabri was h d i d range of about 1% to 20% y Weight and p rary A desized, scoured and bleached control twill fabric polymers include polyvinyl alcohol (PVA), carboxywas padded with 8.1% DMDHEU and 3% of a zinc methyl cellulose (CMC), and starch in the range of about nitrate base catalyst. The fabric was dried and. cured in 1% to 15% by weight. the usual fashion. Results are shown in Table IV.

TABLE I Flo; Grab Tear Wash- Washsample abrasion strength strength wees, wzeflntrii Creaggi Cre2a)s"eh, No. Treatment Warp Fill Warp Fill Warp Fill wash wash wash Wash 507 Control-6.3% sol. DMDHEU plus 2.5% of a zinc 57 118 49.7 54.7 1,367 1,433 5 4.9 5 4.9

nitrate based solution. Desized-scoured. 505 Warp and fil1ing2% PVA plus 2.7% DMDHEU 178 467 62.5 66.5 1,650 1,700 4.7 4.7 4.8 4.6

(and 1% of zinc nitrate based solution) fabric- 3.6% DMDHEU and 1.5% of a zinc nitrate based solution. Desized-seoured. 509 Warp and nu2% PVA plus 2.7% DMDHEU and 777 1,275 90.5 81 2,283 2.117 4.2 4.1 4.9 4.9

TABLE II Flex Grab Tear Wash- Washabrasion strength strength wear, wear, Crease, Crease, Sample 20th 1st 20th No. Treatment Warp Fill Warp Fill warp Fill wash wash Wash waslr 5C7 ControlDesized-scoured, 6.3% DMDHEU and 57 118 49.7 54.7 1,367 1,433 5 4.9 5 4.9

2.5% zinc nitrate based catalyst. 7-P-14. Warp-2.5% polyurethane, 3% PVA2.7 sol. 332 886 68.4 54.7 1,733 1,533 4.5 4.7 4.9 4.7

DMDHEU and 1% of zinc nitrate based catalyst, glelsized-scoured 1.8% sol. DMDHEU untreated 7P2-4. Cured320 F.,desized-scoured,1.8% sol. DMDHEU 990 2,058 88. 2 63.2 2, 533 1,633 4.2 3. 5 4.4 4.3

and 0.5% zinc nitrate based catalyst.

TABLE III [2 x 1 twill, 8.5 z./sq. yd.]

Flex Grab Tear abrasion Strength Strength Sample No. Treatment Warp Filling Warp Filling Warp Filling CRA C7 ControlE6.3% sol. DMDHEU plus 2.5% zinc nitrate solution. Desized- 57 118 49.7 54.7 1,367 1,433 270 scoure 8P1-6 Secured-2.7% sol. DMDHEU plus 1% of zinc nitrate based solution. 1 3,008 3,337 106 1 84 1 3,000 2, 227 243 Warp-3% PVA, 2.4% methylol melamine. Filling untreated. 9P1-6 Scoured2.7% sol. DMDHEU plus 1% zinc nitrate based solution. Warp 1, 473 1, 555 92 70 2, 633 2, 000 255 8% polyacrylate, 3% PVA, 2.4% methylol melamine. Filling untreated.

1 Partial cure on cans.

TABLE IV [2 x 2 twill, 8.5 oz./sq. yd.]

Grab strength Sample Wash- No. Treatment Warp Filling ORA wear Crease 4C8 Control-Desized, scoured,bleaehed. 8.1% sol. DMDHEU and 3% of a 65 53 281 4.7 5.0

zine nitrate based catalyst. 1518 Warp8% polyacrylate, 3% PVA, 1.4% sol. DMDHEU and 0.5% of a 1 87 1 68 1 232 1 4 1 5 zinc nitrate based catalyst. Filling-untreated. Fabricscoured3.6%

DMDHEU and 1.5% of a zinc nitrate based catalyst.

1 Full cure before scouring.

We claim:

1. A process for producing a durable-press fabric with superior abrasion resistance comprising:

(a) treating cellulosic textile warp and filling yarns with an emulsion consisting of about from 4% to 20% by weight of a permanent polymer selected from the group consisting of polyurethanes, polyacrylates, butadiene-styrene copolymers, butadieneacrylonitrile copolymers, and ethylene-vinylacetate copolymers, about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine, and about from 0.5 to 1.5% by weight of a base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured yarns of steps (a); and

(c) crosslinking the woven fabric from step (b) with about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of methylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine.

2. A process for producing a durable-press fabric with superior abrasion resistance comprising:

(a) treating cellulosic textile warp and filling yarns with an emulsion consisting of about from 1% to by weight of polyvinyl alcohol, about from 1% to by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine, and about from 0.5% to 1.5% by weight of zinc nitrate base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured yarns of step (a); and

(c) crosslinking the woven fabric from step (b) with about from 1% to 2% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol met-hoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine.

3. A process for producing a durable-press fabric with superior abrasion resistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consisting of about from 4% to 20% by weight of a permanent polymer selected from the group consisting of polyurethanes, polyacrylates, butadienestyrene copolymers, butadiene-acrylonitrile copolymers, and ethylene vinyl acetate copolymers, about from 1% to 15% by weight of polyvinyl alcohol, about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine, and about from 0.5% to 1.5 by weight of zinc nitrate base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns of step (a) and untreated filling yarns; and

(c) crosslinking the woven fabric from step (b) with about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine.

4. A process for producing a durable-press fabric with superior abrasion resistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consisting of about from 4% to 20% by weight of a permanent polymer selected from the group consisting of polyurethanes, polyacrylates, butadienestyrene copolymers, butadiene-acrylonitrile copolymers, and ethylene-vinyl acetate copolymers, about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine, and about from 0.5% to 1.5% by weight of zinc nitrate base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns of step (a) and untreated filling yarns; and

(c) crosslinking the woven fabric from step (b) with about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea and methylol melamine.

5. A process for producing a durable-press fabric with superior abrasion resistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consisting of about from 1% to 15% by polyvinyl alcohol, about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine, and about from 0.5% to 1.5% by weight of a base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns of step (a) and untreated filling yarns; and

(c) crosslinking the Woven fabric from step (b) with about from 1% to 20% by weight of a crosslinking agent selected from the group consisting of dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine.

References Cited WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R.

8-1163; 117-1394, 139.5 A, 143 A 161 KP, UD, UC, UE