US3560138A - Dyed cellulosic fabric treated with dmdheu in combination with a methylolated triazone - Google Patents

Abstract

IMPROVED TEXTILE CREASEPROOFING COMPOSITIONS ARE PREPARED BY MIXING A TRIAZONE HAVING THE FOLLOWING GENERAL FORMULA:

1-(R1-O-CH2-),3-(R2-O-CH2-),5-R-HEXAHYDRO-1,3,5-TRIAZIN-

2-ONE

WHERE R, IS AN ALKYL OR HYDROXYALKYL RADICAL HAVING 1 TO 6 CARBONS AND R1 AND R2 ARE HYDROGEN OR AN ALKYL RADICAL HAVING 1 TO 4 CARBONS WITH 1,3-DIMETHYLOL-4,5-DIHY DROXYETHYLENE UREA AND ALYLATED DERIVATIVES THEREOF AND AN ACID CATALYST. THE IMPROVED PROPERTIES OF THESE COMPOSITIONS MAKE THEM PARTICULARLY SUITABLE FOR IMPARTING CREASE-RESISTANCE TO FABRICS TREATED WITH SENSITIVE DYES.

Description

United States Patent 3,560,138 DYED CELLULOSIC FABRIC TREATED WITH DMDHEU IN COMBINATION WITH A METH- YLOLATED TRIAZONE Myrtle Joanne Spangler, Danville, Va., assignor to Dan River Inc., Danville, Va., a corporation of Virginia No Drawing. Filed Aug. 1, 1967, Ser. No. 657,512 Int. Cl. D06m 13/14, 13/40; D06p /06 US. Cl. 8116.3 5 Claims ABSTRACT OF THE DISCLOSURE Improved textile creaseproofing compositions are prepared by mixing a triazone having the following general formula:

H 0 In I I 11,0 OI-lgN NCHzORa where R, is an alkyl or hydroxyalkyl radical having 1 to 6 carbons and R and R are hydrogen or an alkyl radical having 1 to 4 carbons with 1,3-dimethylol-4,5-dihydroxyethylene urea and alkylated derivatives thereof and an acid catalyst. The improved properties of these compositions make them particularly suitable for imparting crease-resistance to fabrics treated with sensitive dyes.

This invention relates to improved creaseproofing compositions, methods of treating fabrics therewith and the improved fabrics thereby produced.

The term creaseproofing, as used herein, includes the treatment of fabrics to produce crease-resistant fabrics as well as procedures for providing press-free or permanent press garments. It is well known in the art that fabrics may be treated with certain compositions for the purpose of providing them with a durable shape including pleats, creases, as well as fiat and rounded crease-resistant areas or simply to impart flat crease-resistance thereto. The difference between these two characteristics of treated fabric results from the order of the manufacturing procedure, not the composition and, specifically, the stage at which the fabric is cured during the manufacturing process. Generally, crease-resistant fabrics are impregnated with the treating composition and then dried and cured in a flat condition prior to delivery to the garment manufacturer.

The press-free or permanently shaped and creaseresistant garment is made by impregnating a fabric with the treating composition and then drying the treated fabric with or without partial curing. The steps of drying, and partially curing, if used, are usually combined, however they may be conducted separately, if desired. After a garment is made from the fabric, the crease-resistance and permanent shape are imparted by the garment manufacturer through final curing of the treated fabric after shaping on a press or through a final curing on a form.

It is well known that 1,3-dimethylol-4,S-dihydroxy-Z- imidazolidinone, also called 1,3-dimethylol-4,S-dihydroxyethylene urea and hereinafter referred to as DMDHEU, as well as the alkylated derivatives thereof, are excellent crease-proofing compounds for cellulosic fabrics. However, compositions containing these compounds require relatively rigorous curing conditions, i.e. strongly acidic catalysts and/or high curing temperatures to achieve an acceptable degree of crease-resistance in the fabrics treated therewith. Acidic catalysts such as free acids, acid salts, amine salts, and the like are known to be desirable cata- "Ice lysts for these crease-proofing compositions. The relatively severe curing conditions required by DMDHEU and its alkylated derivatives adversely affect fabrics which have been colored with a sensitive dye. Acid-sensitive and heatsensitive dyes are known to change color during the curing of fabrics pre-dyed therewith, through chemical and/ or physical degradation produced by prolonged acidic and/or high temperature conditions. For example, the blue vat dye, Blue BF, Color Index No. 69825 is known to become slightly green even under mild curing conditions. The susceptibility of this dye to color change causes a serious problem, since subsequent cleaning operations generally result in even greater deviations from the original c0 or.

Although a less sensitive dye may be used sometimes, most often the particular shade desired can be obtained only with the sensitive dye.

Other prior art creaseproofing compositions were narrowly limited to a few compounds which possessed low odor-forming properties. A substantial number of known crease-proofing compounds produce undesirable formal dehyde odors and/or other odors which, in the normal creaseproofing operation as applied to fabrics, had to be washed out after curing. This problem is particularly bothersome in the press-free type fabric operation inasmuch as the final washing of the fabric after final curing in the form of a garment is not feasible.

DMDHEU and its alkylated derivatives are remarkable in not presenting such odor problems and it is for this reason that such materials have been widely accepted by the fabric treating industry. However, as noted above, the curing conditions required for DMDHEU present problems and previous attempts to reduce the effect of curing on certain dyed fabrics treated therewith have been unsuccessful. The requirements of materials used to modify the DMDHEU are limited in the same manner, i.e. they must possess little or no odor-forming properties.

This invention is based on the unexpected discovery that cellulosic fabrics having the above-mentioned advantages can be obtained by impregnating cellulosic fabrics dyed with a sensitive dye with an aqueous solution of DMDHEU and the alkylated derivatives thereof, an acidic catalyst and a triazone having the following general formula:

where R is an alkyl or hydroxyalkyl radical having 1 to 6 carbons and R and R are hydrogen or alkyl radicals having 1 to 4 carbons.

One particularly satisfactory triazone, conforming to the above formula, is 1,3-dimethylol-5hydroxyethyl-tetrahydro-striazone-Z, also called hydroxyethyl triazone. Other examples of triazones from the group represented by the above formula include: 1,3-dirnethoxy-methyl-5- hydroxyethyl-tetrahydro-s-triazone-2; 1,3 diethoxyethyl- S-hydroxyethyl-tetrahydro-s-triazone-Z; 1,3 dimethylol-S- hydroxymethyl-tetrahydro-s-triazone-Z; 1,3 dimethoxymethyl 5 hydroxymethyl tetrahydro-s-triazone 2; and mixtures of these and other compounds conforming to the above-mentioned general formula.

The amount of triazone used to produce the improved compositions of the present invention, may range from about 5% to by Weight of the DMDHEU. The percentage of triazone may be varied in accordance with the 3 particular dye, curing conditions, modifiers, catalyst and the specific triazone selected for use.

Typical cellulosic fabrics which may be creaseproofed by the above compositions include 100% cotton, and blends of cotton with well known synthetic fibers such as polyester fibers, nylon, polymers containing at least 80% polymerized acrynonitrile, such as those commercially available under the trade names Orlon and Acrilan, and so on. Staple synthetic fibers or continuous synthetic filaments can be employed, as desired in ways that are well known in the art. Preferably, the blends contain at least 35 wt. percent cellulosic fibers.

The acidic catalysts most advantageous to the curing of the novel composition include the heretofore mentioned free acids, the acid salts and the amine salts. Specific illustrations of suitable catalysts include phosphoric acid, maleic acid, ammonium chloride, magnesium chloride, zinc nitrate, zinc chloride, ammonium phosphates, sodium phosphates, mono-ethanolamine hydrochloride and the like.

Although the particular conditions and procedures employed to apply the improved creaseproofing compositions of the present invention on the fabric depend on the particular fabric used, the creaseproofing composition and the catalyst are preferably applied to the fabric as an aqueous solution to provide wet pick-ups of 50 to 100 percent based on the weight of the fabric. The concentration of the crease-proofing composition in the impregnating solution preferably ranges from 1 to 60 weight percent. The aqueous solution is conveniently padded onto the fabric under conditions most advantageous to the particular impregnating solution followed as desired by drying and either an immediate curing to impart fiat creaseresistance or a postponed curing to produce permanent press or press-free fabric.

It will be apparent that the impregnating composition can contain other creaseproofing materials, such as tetrahydro 3,5 dimethylol 4H 1,3,5 oxadiazine-4-one, also known as N,N-bis(methylol) uron and 3,5-dimethylol uron and hereinafter referred to as 3,5-dimethylol uron, and alkylated derivatives thereof and the like, urea formaldehyde condensates, dimethylol ethylene urea, and the like in addition to the DMDHEU-triazone combination to impart additional desired properties. In addition to creaseproofing materials, the impregnating solution can contain materials for providing special effects; for example, softeners such as silicones, polyethylene dispersions, cationic surface active agents and the like for adjusting the hand of the fabric to be treated, improved its tear strength and/or sewability; water-soluble polymeric bodiers such as polyvinyl alcohol, modified starch or pre-condensed thermosetting resins such as acrylic resins, etc., for improving the abrasion resistance and tear strength or modifying the hand of the fabric; oil and water repellents such as silicones, fluorocarbon chemicals and the like toimpart resistance to oil-and-water-borne stains; and other additives for imparting special effects.

The drying of the impregnated fabric can be effected under temperature and time conditions over a considerable range. A sufficient reduction in the moisture content of the fabric can be obtained at temperatures of 70 to 300 F. and representative drying times may range from 15 seconds at the higher temperatures, to over one hour at the lower temperatures. If desired, the fabric can be dried without substantial curing to produce a sensitized fabric suitable for making permanent press garments.

Partial curing to produce sensitized fabrics or even complete curing of the impregnated fabric may be conducted simultaneously with the drying operation. Generally, partial curing temperatures include a preferred range of about 240 F. to about 260 F. with a representative partial curing time of about 1 to 5 minutes. The dried, partially cured and the dried, substantially uncured fabrics are capable of being finally cured after assembly into garment form and shaping to produce press-free fabrics.

The final curing, whether conducted at the time of drying or subsequently, is effected by a wide range of temperatures, for example, in the range from 250 to 375 F. with a preferred range of about 300 to about 350 F. Sufficient time for finally curing a dry, partially-cured fabric ranges from about 2 to about 30 minutes and the time range is extended considerably, if the fabric has not been partially cured and/or dried.

Cellulosic fabrics treated with the compositions of the present invention produce superior products which will become apparent from the following examples. In these examples, unless otherwise specified, all parts and percentages are by weight and all temperatures in degrees Fahrenheit. Tear strength determinations were made by the trapezoid method and tensile strength determinations were made by the Grab method. The reflectance determinations were 'made by AATCC Tentative Test Method 110-1964T and Scorch tests were conducted by contacting the fabric sample for 30 seconds with the metal plate of a Scorch Tester (Atlas Electric Devices Co.) maintained at 400 F. and then observing shade change, if any. Crease Resistance determinations were made by the Monsanto Crease Recovery Method (AATCC Tentative Test Method 661959T).

EXAMPLE I A sample of a standard grade, Blue BF (Color Index No. 69825) dyed, cotton fabric was padded to a 70% wet pick up with an aqueous solution of 6.44% DMDHEU and 0.63% zinc nitrate. A second sample of the same fabric was padded at a 7 0% wet pick up with an aqueous solution of 6% DMDHEU, 0.75% hydroxyethyl triazone, 0.45% partially methylated 3,5-dimethylol uron, 0.30% dimethylol urea and 0.63 zinc nitrate.

Each of the above examples was air dried and cured at 340 for six minutes which produced a drastic change in the color of sample #1 to blue-green while the color of sample #2 remained substantially unchanged.

Each of the samples was next subjected to a Scorch test at 400 for 30 seconds, which resulted in a further color change in sample #1 to yellow-green while sample #2 was not affected and continued to remain substantially the original color.

EXAMPLE II Four samples of standard grade, Blue BF dyed cotton fabric, along with corresponding undyed samples for reflectance measurements were prepared by treating with four respective creaseproofing compositions in order to conduct comparative tests as follows:

The aqueous solution used to treat Sample #1 contained the following compounds: 7.5% DMDHEU, 0.63% zinc nitrate and 0.76% sodium acetate and was padded on the cotton fabric at a 70% wet pick up. The sample was dried, and then cured for six minutes at a temperature of 325;

Sample #2 was treated in the same manner as Sample #1 with an aqueous solution containing 6.44% DMD HEU and 0.63 zinc nitrate.

Sample #3 was treated in the same manner as Sample #1 with an aqueous solution containing 4.5% DMD HEU, 1.5% hydroxyethyl triazone, 0.9% partially 'methylated 3,5-dimethylol uron, 0.6% dimethylol urea and 0.63% zinc nitrate.

Sample #4 was treated in the same manner as Sample #1 with an aqueous solution of 4.5% DMDHEU, 3% methylated 3,5-dimethylol uron, 0.63% zinc nitrate and 0.076% sodium acetate.

Except for Sample #4, which had a slight green shade, the samples retained the original color. Each sample was then subjected to a scorch test at 400 for 15 seconds. Only the color of Sample #3 was not affected, while the color of Samples #1, #2 and #4 was changed to yellow.

The samples were then subjected to a series of standard textile tests with the results reported in Table I.

TABLE I Sample number Test conducted:

Crease resistance 305 301 301 296 Tear strength 1.3 1.5 1.5 1.6 Tensile strength 35 31 40 35 Reflectance 76.4 76.2 76.6 77.3

EXAMPLE III Four samples were prepared by treating four patches of standard Blue BF dyed cotton fabric with one of four aqueous creaseproofing compositions respectively. The patches were each padded at 70% wet pick up with one of the following solutions.

SOLUTION I Percent DMDHEU 5 Hydroxyethyl triazone 1.25 Zinc nitrate 0.63 Water Ball.

SOLUTION II Percent DMDHEU 6 Hydroxyethyl triazone 1.00 Zinc nitrate 0.63 Water Ball SOLUTION III Percent DMDHEU Hydroxyethyl triazone 0.75 Partially methylated 3,5-dimethylo1 uron 0.45 Dimethylol urea 0.3 Zinc nitrate 0.63 Water Ball.

SOLUTION IV Percent DMDHEU 6 Hydroxyethyl triazone 0.75 Partially methylated 3,5-dimethylol uron 0.45 Dimethylol urea 0.3 Zinc nitrate 0.47

Each of the samples was dried and then cured at 325 for 6 minutes. Neither the curing nor a scorch test at 400 for 15 seconds changed the color of any of the samples.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the claims.

I claim:

1. A process of preparing a creaseproof cellulosic textile fabric colored with a blue vat dye identified by Color Index No. 69825, impregnating said fabric with a 6 composition comprising an aqueous solution containing a mixture of to by weight of the solids content of said solution of 1,3;dimethylo1-4,S-dihydroxyethylene urea and 35% to 10% by weight of the solids content of said solution of a compound having the formula:

r- R10 CHQN N-CHzORz wherein -R is selected from the group consisting of alkyl and hydroxyalkyl groups having 1 to 6 carbon atoms and R and R are selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms, drying and curing the impregnated fabric in the presence of an acidic catalyst to produce a creaseproof fabric whereby the color of said dye is substantially unaffected by drying and curing.

2. The process as claimed in claim 1 wherein said catalyst is zinc nitrate.

3. The process as claimed in claim 1 wherein said compound is 1,3-dimethylol-5-hydroxyethyl-tetrahydro-striazone-Z.

4. The process as claimed in claim 1 wherein said compound is 1,3-bis(methoxymethyl)-5-hydroxyethyl-tetrahydro-s-triazone-Z.

5. Creaseproof colored cellulosic textile treated by the process claimed in claim 1.

References Cited UNITED STATES PATENTS 2,901,463 8/1959 Hurwitz 8116.3X 3,049,446 8/1962 Goldstein et al. 8116.3X 3,350,162 10/1967 Beck et a1 81l6.3X 3,401,006 9/1968 Perrino 8--116.3 3,425,208 2/1969 Shippee et a1 8l16.3

FOREIGN PATENTS 903,797 8/1962 Great Britain 8-116.3 927,166 5/1963 Great Britain 8-116.3

OTHER REFERENCES I. T. Marsh, Crease Resisting Fabrics, Reinhold, New York, 1962, p. 75.

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R.