|Numéro de publication||US2268273 A|
|Type de publication||Octroi|
|Date de publication||30 déc. 1941|
|Date de dépôt||27 mai 1939|
|Date de priorité||27 mai 1939|
|Numéro de publication||US 2268273 A, US 2268273A, US-A-2268273, US2268273 A, US2268273A|
|Inventeurs||Wilkes Benjamin G, Wilson Alexander L|
|Cessionnaire d'origine||Carbide & Carbon Chem Corp|
|Exporter la citation||BiBTeX, EndNote, RefMan|
|Référencé par (24), Classifications (16)|
|Liens externes: USPTO, Cession USPTO, Espacenet|
Patented Dec. 30, 1941 UNITED STATES PATENT OFFICE TEXTILE FINISHING tion of New York No Drawing. Application May 27, 1939, Serial No. 278,122
The invention relates to textile finishing, and in particular to compositions and a treatment for improving the softness, pliability, draping qualities, and other characteristics of textile fibers, yarns, threads and fabrics. It is especially concerned with means for improving the quality of fabrics composed entirely or in large part of cellulose or cellulose derivatives.
The improvement of textile materials by treatment with substances known as softening or finishing agents is not a new expedient, but it had" assumed additional importance with the intro= duction and increasing use in the textile art of artificial oellulosic fibers. By permeating or impregnating cellulosic fabrics, yarns, threads and the like with very small quantities or a suitable finishing material, it has been found possible to improve substantially the softness, pliability and other qualities oi such products, which enhances their appearance, hand and general attractiveness to the consumer. Substances heretofore proposed in the art for such finishing treatment have not been entirely satisfactory. In many cases they have been only partially et fective in their softening action, and, through inability to be completely and firmly adsorbed by the fiber, generally have lacked permanency and resistance to extraction by washing or other cleaning operations. ()ther objections in pre vious finishing agents include their required use in large and expensive quantities, the tendency to impart a greasy or otherwise undesirable surface on the fiber, or, in the case of some sub-= stances, interference with the dyeing properties of the textile.
It is an object of the present invention to provide improved textile finishing compositions, which are largely free from the above-mentioned disadvantages, and which are capable in a fiber or fabric treating process of effecting a more permanent and satisfactory softening action. A further object is to produce in cellulosic fabrics, yarns, threads, and like products, an improved fullness, softness, pliability and hand, which enhances the general adaptability and use of such products in the textile art.
The above objects are accomplished through the use as finishing or softening agents of a group of organic compounds consisting of glyoxalidines and certain of their derivatives.
These substances in very dilute aqueous solutions are capable of imparting an excellent, and relatively permanent softening efiect on textile materials. Glyoxalidines may be regarded as dehydration products of certain amides, and they may be obtained by reacting polyamines and the higher carboxylic acids under certain conditions. The manner of forming the compounds forms no part of the present invention, but their preparation can be represented by the following scheme:
0 l R.-OH+H:N.CH.CH.NH.R:.X H:O l 1 R1 R1 Fatty acid alkylenc polyamine Amide wherein R is an aliphatic group containing from it to 20 carbon atoms representing the residue of a higher fatty acid; R1 represents hydrogen or a lower alkyl group; Ra represents an alkylene group or a lower alkyl substituted alkylene group; and X represents a hydroxyl group, an amino group or an amino-alkylene substituted imino group.
Within the scope of the present invention there are included as operative compounds any of those falling within the above ring formula, which may be broadly termed 1,2-disubstituted glyoxalidines, and in which substitution also may be made in one or both of the 4 and 5 positions. To promote solubility, or create desired pH effects, salts of these glyoxalidines may be used, in place of the free bases, in preparing the treating bath, or the compounds may be dissolved in the presence of acids. Quaternary ammonium salt derivatives can be prepared by reaction with an organic ester, and acids will react to form addition products. Since some glyoxalidines within the above formula may possess more than one basic group, the particular nitrogen group neutralized by the addition of, say, one mole of acid, cannot be indicated by a general specific structure, but for the purpose of the present invention, the (acid addition) products, as well as the quaternary salt derivatives, may be considered to include compounds of the following general structure:
in which R, R1, R2 and X are as indicated in the above formula; Y represents an'organic or inorganic acid radical, and R: is hydrogen, or an alkyl or aralkyl group. Reaction products with either acids or inorganic esters are intended to be included within the broad reference herein to salt derivatives of the glyoxalidines, and suitable salt-forming substances are acids such as formic, acetic, and hydrochloric acids, or inorganic esters represented by the compounds dimethyl sulfate, diethyl sulfate, methyl iodide, and benzyl chloride.
Typical specific compounds within the above formulae which have shown an excellent softening and finishing action are:
Example 1 HOCIHA- H:
l-hydroxyethyl-zheptadecyl glyoxalidine l-hydroxyethyl-2-heptadecyl glyoxalidin was prepared by reacting 424 grams of hydroxyethyl ethylene diamine with 568 grams of stearic acid, in the presence of 400 cc. of xylene. The mixture was refluxed and water continuously removed from the condensate. In 12 hours 60 grams of water were thus collected and the temperature reached 187 C. at the completion of the reaction. The xylene was distilled off at 25 mm. pressure, and the excess hydroxyethyl ethylene diamine recovered by distillation to 200 C. at mm. pressure. A portion of the l-hydroxyethyl-2-heptadecyl glyoxalidine thus formed was converted to the acetate by melting 350 grains of the compound with 60 grams of glacial acetic acid. and another portion of :350 grams was reacted with 154 grams of diethyl sulfate at 100 C. to form the compound l-hydroxyethyl-lethyl-Z-heptadecyl glyoxahdonium ethylsulfate.
aaoasve These glyoxalidine compounds may be represented by the following formulae:
l-hydroxyethyl-Z-heptadecyl glyoxalidonlum acetate Calla-=0 CH:
HOCzHr-N Hz 7 l-hydroxyethyl-l-ethyl-2-heptadecyl glyoxalidonium ethyl sulfate Aqueous solutions of these compounds were made with a concentration of 0.25% of the finishing agent, and with adjustments to a pH value of both 4.5 and 6.5. Pieces of rayon fabric, previously scoured, were immersed in these solutions for 5 minutes, with the temperature of the bath at C. They were then removed, passed through squeeze rolls and dried on a mangle. The treated samples were evaluated in point of hand" or softness, and in each of them the improvements in the pliability, draping qualities, and softness were readily apparent. The solutions having a pH value of 6.5 exerted a slightly greater softening action than those of higher acidity, but an improved textile quality was imparted by each treatment.
Example 2 /N\ oi1nuo on,
HsNC:H4N H1 l-aminoethyl-Z-heptadecyl glyoxalldlne CnHu-C CH:
H:NC:H|N H: l-aminoethyl-Z-heptadecenyl glyoxalldine Following reaction conditions substantially similar to those of Example 1, the compounds 1- aminoethyl-Z-heptadecyl glyoxalidine and 1- aminoethyl-Lheptadecenyl glyoxalidine were prepared by reacting diethylene triamlne with stearic acid and oleic acid, respectively. Addition products of these glyoxalidines were readily formed by further reaction with acids or alkyl salts such as dimethyl sulfate, and in this mannor the following derivatives were prepared:
Water solutions of each of these compounds, in a concentration of 0.50%, were made, and skelns of jute yarn were immersed in the solutions for a period of minutes, at a solution temperature of 80 C. The skeins were then passed through a squeeze roll and air-dried. A definite softening action and improvement. in pliability was readily detectable in the yamlsample treated by each solution, although the finishing action of the stearic acid derivatives was slightly better than that of the others.
Example 3 A series of compositions was prepared, including some of the compounds illustrated in the two above examples, and others within the general class 'of the described aminoethyl and hydroxyethyl heptadecyl glyoxalidines. Samples of rayon, cellulose acetate, cotton and jute fabrics were treated by soaking in 0.5% aqueous solutions of these compounds, acidified with acetic acid to a pH of 6. The temperature of each solution was 60 to 70 C. and the immersion period was 6 minutes. After wringing and drying the samples, they exhibited a noticeable softening effect in all instances, which was particularly evident in the cellulose acetate and jute fabrics. The pH value of the soaking solutions was found to be reduced to 5.7 to 5.8, suggesting the selective removal of the glyoxalidine from the solutions.
As will appear from the above examples, these new. finishing agents are readily adsorbed by textile fibers, and are effective in concentrations from about 0.1% to 1.0% by weight in a water solution or dispersion. Minute quantities of the glyoxalidine compound permeat the textile without leaving a greasy or other extraneous feel. and their resistance to hydrolysis or removal by washing creates a substantially permanent softening efiect. In addition to producing a softer and more pliable fiber or fabric, these finishing agents render the material more substantive to direct dyes, or, where dyeing is effected before the finishing treatment, they improve the fastness of the dye to washing. Water solutions varying over a wide range of acidity or alkalinity may be used, and the proper functioning of the glyoxalidine derivatives is not affected by hard water or the presence of lime salts. A preferred application of the invention is in the treatment of textiles composed entirely, or in large part, of cellulose or cellulose derivatives. Cotton goods are remarkably improved by these new finishing agents, and rough materials, such as denim, show a novel draping quality and softness after treatment. A most important present use of the invention is in the treatment of rayon textiles, whereby a transformation in texture is effected more nearly resembling that of natural silk. A similar action is shown on unsized paper and wood-fiber goods.
"Many glyoxalidine derivatives other than those specifically described are of contemplated use for the purpose of the invention, and various alkylene polyamines may serve as the starting material in the preparation of these compounds. These include diethylene triamine, triethylene tetramine, hydroxyethyl ethylene diamine, dipropylene triamine and tripropylene tetramine. The hydroxyalkyl glyoxalidine derivatives have shown an especially effective textile softening action. The acids used in the glyoxalidine preparation may include generally the saturated or unsaturated fatty acids having 12 or more carbon atoms, and comprising lauric, palmitic, oleic, linoleic, ricinoleic, and stearic acids. Numerous modifications with respect to the operative and suitable compounds are within the scope of the invention as defined by the appended claims.
The glyoxalidine compounds themselves and their method of preparation, are claimed in the copending applications of A. L. Wilson, Serial Nos. 191,191 and 285,081, filed February 18, 1938 and July 18, 1939 respectively.
1. Process of finishing and softening textile materials which comprises applying to said materials a compound of the group consisting of substances of the formula N R-C CH.R1 XR2l I--( 3H.R1
(wherein R is an aliphatic group containing from 10 to 20 carbon atoms representing the residue of a higher fatty acid; R1 is one of the group consisting of hydrogen and lower alkyl radicals; R2 is one of the group consisting of alkylene and lower alkyl substituted alkylene radicals; and X is one of the group consisting of hydroxyl, amino and amino-alkylene substituted imino radicals); and salt derivatives of these substances.
2. Process of finishing and softening cellulosic fibrous materials, which comprises applying to said materials and adsorbing thereon a finishing agent composed of a compound of the group consisting of substances of the formula GH.R1
, (wherein R. is an aliphatic group containing from X is one of the group consisting of hydroxyl,
amino and amino-alkylene substituted imino radicals); and salt derivatives of these substances.
3. Process of finishing and softening cellulosic fibrous materials, which comprises applying to said materials and adsorbing thereon a finishing agent, by immersion in an aqueous solution containing about 0.1% to 1.0% of a compound of the formula R-C/ crmn X-RgN- H-R wherein R is an aliphatic group containing from 10 to 20 carbon atoms representing the residue of a higher fatty acid; R1 is one of the group consisting of hydrogen and lower alkyl radicals; R2 is one of the group consisting of alkylene and lower alkyl substituted alkylene radicals; and X represents a hydroxyl radical.
4. Process of finishing and softening cellulosic fibrous materials, which comprises applying to said materials and adsorbing thereon a finishing agent, by immersion in an aqueous solution containing about 0.1% to 1.0% of a compound of the formula wherein R is an aliphatic group containing from 10 to 20 carbon atoms representing the residue of a higher fatty acid; R1 is one of the group consisting of hydrogen and lower allwl radicals; R2 is one of the group consisting of alkylene and lower alkyl substituted alkyiene' radicals; R3 is one of the group consisting of alkyl and aralkyl radicals; X is one of the group consisting of hydroxyl, amino and amino-alkylene substituted imino radicals; and Y is one of the group consisting of fatty acid, alkyl sulfate and inorganic acid radicals.
5. A soft, pliable textile material composed of or containing cellulosic fibers having intimately associated therewith and strongly adsorbed therein a finishing agent composed of a. compound of the group consisting of substances of the formula (wherein R is an aliphatic group containing from 10 to 20 carbon atoms representing the residue of a higher fatty acid; R1 is one of the group consisting of hydrogen and lower alkyl radicals; R: is one of the group consisting of alkylene and lower alkyl substituted alkylene radicals; and X is one of the group consisting of hydroxyl, amino and amino-alkylene substituted imino radicals) and salt derivatives of these substances.
6. A soft, pliable textile material composed of or containing cellulosic fibers having intimately associated therewith and strongly adsorbed therein a finishing agent composed of a compound of the group consisting of substances of the formula /N\ R(IJ/ 0mm x-n zg onai wherein R is an aliphatic group containing from 10 to 20 carbon atoms representing the residue of a higher fatty acid; R1 is one of the group consisting of hydrogen and lower alkyl radicals; R:
is one of the group consisting of alkylene and lower alkyl substituted alkylene radicals; and X represents a hydroxyl radical.
'7. A soft, pliable textile material composed of or containing cellulosic fibers having intimately associated therewith and strongly adsorbed therein a finishing agent composed of a compound of the group consisting of substances of the formula
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|Classification aux États-Unis||442/102, 554/51, 554/59, 8/130.1, 548/350.1, 8/189, 548/348.1, 252/8.63, 8/573|
|Classification internationale||D06M13/35, D06M13/473, D06M13/00|
|Classification coopérative||D06M13/473, D06M13/35|
|Classification européenne||D06M13/473, D06M13/35|