US3160469A - Biscarbamate-formaldehyde adducts for wrinkle resistance finishes - Google Patents

Description

United States Patent 3,160,469 BISCARBAMA'I'E-FORMALDEHYDE ADDUCTS FOR E RESISTANCE FINISHES Sidney L. Vail, Cliiford M. Moran, and John D. Reid,

New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture N Drawing. Filed July 19, 1962, Ser. No. 211,141 5 Claims. (Cl. 8-4163) (Granted under Title 35, US. Code (E52), sec. 266) 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.

This invention relates to the treatment of cellulosic textile materials to produce textiles having improved properties. More specifically, the present invention relates to new textile treating agents and a method of treating cellulosic textile fabrics With these agents whereby the fabrics are rendered resistant to wrinkling, have improved resiliency, and possess wash-and-wear properties.

Moreover, the finishes produced from the new textile" treating agents of this invention were found to be extremely durable. These finishes were found to effectively resist hydrolytic removal under conditions that remove the finishes based on the commonly used N-methylol treating agents.

In general, the production of wrinkle resistant and wash-and-Wear fabrics has been accomplished by the use of diand polyfunctional N-methylol finishing agents. These agents are generally formed by the addition of formaldehyde to ureas (cyclic or straight chain), melamine, and other similar type compounds. However, it is well known that finishes produced from the agents are fairly easily removed by repeated washing procedures which employ moderately strong acidic solutions, that is, the souring step used in most commercial launderings. After such treatments, it is often found that the treated fabric has generally lost the finish and the desired wrinkle resistance and wash-and-wear properties. these treating agents can not be used to produce acceptable wash-and-wear cellulosic fabrics which are to be subjected to these, or similar, hydrolytic conditions. In general, alkalinev hydrolysis is somewhat less detrimental than acidic hydrolysis under the normal conditions encountered in use.

In copending application Serial No. 204,013, filed June 20, 1962, of Sidney L. Vail, John J. Frick, Jr., and Wilson A. Reeves, creaseproofing agents comprising bisformamide-formaldehyde adducts are described. Although this process produces wrinkle-resistant and wash-and-wear fabrics of high resistance to harsh conditions of acidic hydrolysis, the treated fabrics are susceptible to damage from hypochlorite bleaching agents. Consequently, these creaseproofing agents cannot be used on all fabrics. Ethyl carbamate-formaldehyde adducts have been shown previously [American Dyestuif Reporter 50, p. 849 (1961)] to be an effective agent for producing treated .cotton fabrics which are wrinkle-resistant. Also, it was noted in this work that some carbamate finishes retained chlorine after hypochlorite bleaching, but that these finished fabrics were not susceptible to chlorine damage. It was considered that the N-methylol derivatives of biscarbamates would form new finishes on cellulosic fabrics which would prove to bemore highly resistant to acid hydrolysis than those finishes based on ethyl carbamate. Also, it was considered that many of the advantages, such as resistance to chlorine damage, of the finishes based on Consequently,

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such a treatment whereby the finish produced is resistant to harsh conditions of acidic hydrolysis. Also the treated fabric may be laundered repeatedly by ordinary procedures, which procedures may include the use of hypochlorite bleaching agents, Without suffering discoloration or significant loss in strength in the laundering procedure or subsequent treatment.

In general, these and other objects of the invention are accomplished by treating the cellulosic textile with an aqueous solution containing the N-methylol derivatives of bicarbamates having the following structure:

The bicarbamate-formaldehyde adducts used for the treatment of the cellulosic textile in the process of this invention can be obtained by the reaction of a biscarbamate of the above-described structure and formaldehyde- It is prein aqueous media under alkaline conditions. ferred to use an excess of formaldehyde in this reaction, the excess being about one to two molar equivalent of free formaldehyde based on the presumption that all amido NH groups will methylolate to form N-methylol; groups. Thus, although two molar equivalents of formaldehyde would theoretically fully methylolate the biscar- V bamates of the above-described structure, it is preferable to have about three to four molar equivalents of formaldehyde for the reaction with the biscarbamates. The chemical effect of the excess formaldehyde is not definitely known; however, in general, it appears that some formaldehyde is reacting with the cellulose to form methylene ether crosslinks in addition to the crosslinking through the nitrogenous agent. An amount of formaldehyde significantly in excess of the four to one ratio can also be employed, but it is inefiicient and uneconomical to use' such a large excess. The other conditions of this reaction are well-known in the trade. Generally, heating the alkaline, aqueous solution of the biscarbamate .and formaldehyde at 60 C. for 3.0 minutes or allowing the solution to stand at room' temperature (2025 C.) for 18-24 hours is suificienttoachieve formation of the N-methylol derivatives. The reaction products thus producedv are water soluble. The solution can be used as is or can be diluted with water for treatment of the cellulosic material.

Prior to application of the agent to fabric, an acidic substance or a substance producing acidity at elevated temperatures is added to the diluted solution to serve as particular textile processing conditions used, the type of textile being treated, and the properties desired in the finished textile. Generally, it is preferred to use from about 5% to 20% by weight of the reactants in the' diluted treating solution. The catalysts which may be Xcess liquid is mechanically removed, and the wetted' :xtile is dried and cured. Following the curing operaion, it is preferable but not absolutely necessary, to afterlash the treated textile in a slightly alkaline, aqueous olution to remove any unreacted materials.

The processes of this invention can be used to treat sub tantially any hydrophilic fibrous cellulosic material such s cotton, rayon, ramie, jute, and the like which can e'impregnated with a liquid, dried, and cured.

The following examples are given by way'of illustraon and not byway of limitation of the invention. The etailed procedures given below in the examples are illusrative, and are not'the only or specific conditions for the roduction of an acceptable finished textile. Many variafons or additions within these procedures can be made, will be readily apparent to those skilled in the art. In 1e examples, all percentages are by weight. The fabrics 'ere tested by the following methods: wrinkle recovery ngle, Monsanto method, American Society for Testing daterials (ASTM) test D1295-53T; breaking strength, \STM test D39-49 damage caused by retained chlorine,

tmerican Association of Textile Chemists and Colorists,

:ntative test method 92-1958T.

EXAMPLE 1 A weighed portion of thebiscarbamate was dissolved 1 an alkaline, aqueous solution of formaldehyde such that re molar ratio of formaldehyde to the biscarbamate was djusted to about 7 with dilute hydrochloric acid. Then,

From about 0.5% to about a weighed portion of magnesium chloride hexahydrate 'as added such that its final concentration in the padding )lution was about 4%. amate (prior to methylolation) in the padding solution 'as about 5% Using this general procedure, with variaons noted where appropriate, the following carbamates we used to produce various padding solutions:

olution A: Methylenebis(ethyl carbamate). olution B: Methylenebis(ethyl carbamate), with a cata lyst of 1% zinc fiuoborate. i

olution C: Ethylenebis(ethyl carbamate).

olution D: Ethylidenebis(ethyl carbamate). olution E: Methylenebis (methyl carbamate), with a catalyst concentration (if-2%, the catalyst composed of 60% citric acid and 40% magnesium chloride hexahydrateJ olution F: A 12% dimethylol ethyl carbamate solution was prepared using the general procedure outlined.

above except the solution was allowed to stand at20- 25 C. for a period of about 20 hours.

EXAMPLE 2 Concentration of the biscar are i A sample of x 80 cotton print fabric was dipped in Table 1 PROPERTIES OF TREATED FABRICS Wrinkle Re- Breakin g covery Angle Strength Fabrics From Soluti0n (warp only), Retained After degrees Scorch-Test,

Percent A 126 99 183 99 139 92 125 91 130 95 F 125 1 Untreated Fabric EXAMPLE 3. The durability of some of the finishes to acidic hydrolysis was tested by treating the fabrics for thirty minutes at 80 C, in a solution containing 1.5% phosphoric acid} and 5% urea. The results of this hydrolysis on properties of the treated fabrics are given in Table II.

' Table II' v ACID HYDROLYSIS OF OARBAMATE FINISHES Percent of Wrinkle Re- Original covery Angle Fabrics From Solution Nitrogen (warp only),

. Retained After degrees Hydro1ysis finishing process for rendering a celcontains from 5 to 20% by weight of the reaction product offorrnaldehyde and a biscarbamate represented by the formula:

0 0 H H E Roo.N cn'H)..No0R

wherein n is an integer of 'one to four, R is an alkyl groupv of from 1 to 4 carbon atoms, and R is a member of the group consisting ofH and'an alkyl group of from 1 to.4 carbon atoms, and from 0.5 to 5%. by weight of an acid'catalyst and heat curing the thus impregnated cellulosic textile materials 2. The process of claim 1 wherein the biscarbamate is methyleneb is(methyl carbamate). I v

3. The process of claim '1 wherein the biscarbamate is methylenebis(ethylcarbamate).

l 4. The process of claim 1 wherein the biscarbamate is ethylidinebis(etl1yl carbamate). i w

5. The process of claim 1 wherein the biscarbamate is ethylenebis (ethyl carbamat e) References Cited .by the Examiner V UNITED STATESPATENTS 2,306,185 12/42 Pikl 260-482 2,385,911 10 45 Chenicek 260-72 2,386,141 10/45 6 Rogers '8-l16.3 2,518,444" 8/50. Baird er a1 260-72 2,774,746 12/5 Shelly 8116.3 2,899,263 8/59 'Neussl'e et ai. 8--116.3 2,904,387 9/59 Hollbrook et a1. 8-'116.3' 2,926,190 A 2/60 Wasson'et a1. 2601482 2,954,39 9/60 "Ayers et a1. 260, 4s2

I I FQREIGN PATENTS I 7 508,202 7/52. 'Belgium. 6

NORMAN o, TORCHIN, Primary Examiner. ABRAHAM H. WINKLESTEIN, Examiner.

Claims (1)

1. A CHEMICAL FINISHING PROCESS FOR RENDERING A CELLULOSIC TEXTILE MATERIAL WRINKLE RESISTANT, THE WRINKLE RESISTANCE FINISH BEING CHARACTERIZED BY RESISTANCE TO ACID HYDROLYSIS AND RESISTANCE TO THE DAMAING EFFECTS OF HYPOCHLORITE BLEACHING AGENTS, COMPRISING IMPREGNATING AA CELLULOSIC, TEXTILE MATERIAL WITH AN AQUEOUS SOLUTION THAT CONTAINS FROM 5 TO 20% BY WEIGHT OF THE REACTION PRODUCT OF FROMALDEHYDE AND A BISCARBAMATE REPRESENTED BY THE FORMULA: