US3079279A

US3079279A - Blends of imidazolidinones and aminoplasts and method for finishing cellulose containing textile material

Info

Publication number: US3079279A
Authority: US
Inventors: Jr William J Van Loo
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1961-02-03
Filing date: 1961-02-03
Publication date: 1963-02-26
Anticipated expiration: 1980-02-26
Also published as: NL276154A; NL275422A; BE615320A; FR1317893A; BE614586A; NL275872A; BE614590A; BE615426A

Description

3,079,279 BLENDS 6F IMiDAZOLIDWONES AND AMINO- PLASTS AND METHOD FQR FlNlfiHlNG CELLU- LGSE CONTAINHNG TEXTiLE MATERKAL Willianrll. Van Loo, in, Middlesex, N.J., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed Feb. 3, 1961, Ser. No. 86,86!) 6 Claims. (Cl. 117139.4)

This invention relates to a novel combination or blend of water soluble textile finishing materials, to the process for applying them to textile materials and to the textile materials finished therewith. More particularly, this invention relates to novel blends of imidazolidinones and aminoplast resins having particular utility in the finishing of cellulose containing textile materials and to the cellulose textile materials finished therewith.

With the ever-increasing use of wash and wear fabrics, the textile finishing industry is constantly on the alert for the development and use of new finishes for textile materials and in particular cellulose containing textile materials. The use of various textile finishing resins and/ or agents alone or in combination with other resins and/or agents to achieve various additive effects has been employed for many years by those skilled in the art of textile finishing. However, many such combinations have marked deficiencies even though upon application they produce additivebeneficial effects. Some of these deficiencies, including poor compatibility or stability, effect on fabric color, degradation of fabric strength upon application and curing, degradation of fabric strength upon laundering or heat treatments, that is, calendering, embossing, glazing, ironing and the like, and in addition poor resistance to chlorine bleaches plus the adverse effect of such finishes on the hand or feel of the finished fabric, have in many instances limited the proposed use of various combinations for specific additive effects.

It is the particular object of the present invention to provide a novel blend of textile finishing resins or agents which, when applied in the finishing of cellulosic textile materials, produce a synergistic effect rather than a merely additive one, both with regard to increased wrinkle recovery and less degradation of the fibers when scorched subsequent to chlorine bleaching.

It is a further object of the present invention to provide a novel blend or combination which is characterized by good compatibility and stability, minimal effects on fabric color, and which is otherwise generally satisfactory for employment in the textile finishing industry.

These and other objects and advantages of the present invention will become more apparent from the detailed description thereof set forth hereinbelow.

In accordance with the present invention, I have found that when a novel combination of chemicals consisting of an imidazolidinone of the formula:

where the values of R may be the same or different and are selected from the group consisting of hydrogen and lower alkyl such as methyl, ethyl, propyl and butyl and X is a member selected from the group consisting of O and S, is combined with an aminoplast resin and ap plied to cellulose containing textile materials in certain proportions, quite surprisingly an increase in wrinkle recovery is obtained with less fiber degradation when scorched subsequent to chlorine bleaching, when com- 3,979,279 Patented Feb. 26, 1953 pared to resin finishes resulting from the use of the individual resins alone.

Additionally, the invention relates to the use of such compositions in the finishing of cellulosic textile materials and to the cellulosic textile materials so finished.

By the term aminoplast, as it is employed herein, it is meant aldehyde, and in particular formaldehyde, condensation products of polyfunctional compounds characterized by the presence of amino (-NH and imino (:NH) radicals in their molecules. The aminoplast resins employable in the blends of this invention should be characterized by the presence of more than one methy-lol group (the result of condensation between a mole of formaldehyde and a labile hydrogen of an amino or imino radicals) to insure maximum effects in accordance with this invention.

By the term cellulose containing textile material it is meant fibers, filaments, yarns, fabrics, whether woven or non-woven, knitted, felted or otherwise formed, containing at least 50% of cellulose fiber such as cotton, rayon, linen, hemp, jute or the like. The cellulose fibers may be present in combination with other natural or synthetic fibers, such as wool, silk, acetate, nylon, polyester fibers, acyrlic fibers and the like. Preferably, the textile material is a formed, woven cotton fabric.

Lmidazolidinones having the formula above are prepared by reacting a urea with glyoxal or a substituted glyoxal by procedures to be described later.

A particular prefer-red class of imidazolidinones for use in this invention are those having the following general formula where the R values may be the same or different and are selected from the group consisting of hydrogen and lower alkyl such as methyl, ethyl, propyl and butyl and X is a member selected from the group consisting of oxygen and sulfur.

Compounds of the preferred class of imidazolidinones set forth in the general formula above Where R and R are hydrogen are prepared by reacting a urea with glyoxal under such conditions that both carbonyl groups of the dialdehyde react with amide groups of the urea.

If the substituted glyoxais are used, products where R, and/or R are alkyl result.

Illustrative of the ureas which may be used are urea, l-methylurea, l-ethylurea, l-n-propylurea, l-n-butylurea, 1,3 d-imethylurea, 1,3 diethylurea, 1,3 di n propylurea, 1,3-di-n-butylurea, l-methyl-3-ethylurea, 1,3-di-secbutylurea, l-allylurea, 1,3-diallylurea, and the like.

Illustrative of the glyoxals which may be used are glyoxal, methyl glyoxal, ethyl glyoxal, n-propyl glyoxall, isobutyl glyoxal, dimethyl glyoxal, methyl ethyl glyoxal, ethyl propyl glyoxal, and the like.

The ureas and glyoxals are normally reacted in stoichiometric amounts at room temperatures (about 20 to 30 C.) although slight excesses of either of the reactants may be employed. This reaction may be carried out at temperatures from between 0 and (2., though preferably temperatures of about 20 to 70 C. are employed and of course the reaction may be carried out at atmospheric, subatmospheric or superatmospheric pressures for times sufficient to complete the reaction. Completion of the reaction is normally indicated by complete usage of glyoxal as shown by glyoxal determinations in the reaction mixtures.

Wherein the compounds R and R are lower alkyl.

these are made by reacting the corresponding compounds Where R and R are hydrogen with an appropriate lower alcohol under acidic conditions. Any of the strong acids normally employed in the alkylation or etherification of amide-formaldehyde condensates or aminoplast resins may beemployed. Such acids include the strong mineral acids, such as sulfuric, hydrochloric, nitric and the like. Normally, 'suiiicient acid is employed to produce a pH of below 4. Suitable alcohols may be any of the lower alcohols such as methanol, ethanol, the propanols, the butanols and the like. The reaction with an alcohol is carried out at a temperature of between and 50 C. and preferably at 15 C. to 30 C. for from about 2 minutes to 10 minutes, the shorter times being at the higher temperatures. It is for the most part impractical to carry out the reaction below 0 C; and at temperatures above 50 C. there is danger of polymerization. Preferably, 2 moles or more of alcohol is employed per mole of imidazolidinone to insure full alkylation, any excess present being used as solvent for the reaction.

The aminoplast resins suitable for use in blend with the imidazolidinones referred to above are principally any of the aminoplast creaseproofin-g resins known to the textile finishing industry. Such resins include the melamine-formaldehyde condensates as probably the single most important group. Suitable melamine-formaldehyde condensates include those having from 1 to 6 moles of combined formaldehyde and from 1 to 6 moles of combined alcohol, such as, for example, methyl, ethyl and the like, although in addition to aliphatic monohydric alcohols, polyhydric alcohols and ether alcohols are also contemplated. Examples of such resins and how they are prepared may be found in US. Patent No. 2,197,357 and US. Patent No. 2,529,856. As noted above, preferably such creaseprooiing resins are fully water soluble and essentially monomeric potentially thermosetting materials. Examples of such materials include tris(methoxymethyl) melamine, tris(methoxymethyDdimethylol melamine, hexakis(methoxyrnethyl) melamine and the like.

Urea-formaldehyde condensates are contemplated, such as dimethylol urea, alkyla ted dimethylol urea such as methylated dimethylol urea, dimethylol ethylene urea, dimethylol 1,2-propylene urea, dimethylol 1,3-propylene urea and other related homologous compounds. Additionally the formaldehyde condensates of dicy'andiamide, biuret and the like are contemplated, as are the Water soluble formaldehyde condensates of thiobisamides described in US. latent No. 2,887,408.

Guanamine-formaldehyde condensates, as for example, those described in U.S. Patent No. 2,887,409 including the formaldehyde condensates of methoxyacetoguanaminc, .ethoxyacetoguanamine, tertiary butoxy acetoguanamine andlthc like are contemplated. I

Urons, such as, for example, N,N-bis(methoxymethyl) uron and variousother and closely related compounds such as are described in US. Patent No. 2,373,135 are contemplated. Additionally, tetrahydrotriazohes such as tetrahydro-S-(beta-hydroxyethyl)-- triazone and related compounds that are described in U.S Patent No. 2,304,624 are contemplated.

In addition to the above examples, the triazines such as are described in US. Patent No. 2,373,135 are contemplatecl.

These exemplary creaseprooiing resins may be employed singly or in combination with each other and with other creaseproofing resins known to those skilled in the art, in accordance with the present invention.

The imidazolidinones and the aminoplast resins or mixtures of imidazolidinones and aminoplast resins must be employed in relativearnounts in 100 parts of resin solids of between from about 20 to about 80% of the .imidazolidiuone andfrom about 80 to about 20% of the aminoplast resin. Thus, from between about 1:4 to" about 4:1 imidazolidinone to aminoplast constitutes the range on a Weight basis in which the effects of the novel-'- blend of this invention are demonstrable.

The novel resinous composition of this invention containing the imidazolidinones and aminoplasts in the aboveclescribed relative proportions may be applied to cellulosic textile materials by any of the conventional techniques such as immersion, padding, spraying and the like followed Where necessary by squeezing, hydroextraction or similar processes in order to aifix the desired amount of solids on the fabric.

The method of application should be such that from about 1 to about 25% and in some instances higher amounts of the product of this invention based on the weight of the fabric are deposited thereon. Within certain limits, the amount of agent applied depends upon the particular type of fabric being treated. Thus, when treating fabric consisting of fibrous cellulosic materials, the concentration of the order of about 1 to 25% and more particularly from 3 to 10% solids, based on the dry weight of the fabric, may be employed.

The catalyst or accelerator employed is an acidic type catalyst and may be a free acid, acid salt, alkanolamine salt, metal salt and the like of the type well known to thosein the textile finishing art. The concentration of catalyst employed may range from about 0.1 to about 25% .or'

higher, based on the Weight of the resin solids, depending uponjthe particular catalyst type employed. Thus, for example, from between about 0.1% and about 10% of a free acid such as phosphoric, tartaric, oxalic or the like m be employed, while in the case of ammonium chloride amounts of from between 0.5 and about 10% are used. In the case of amine salts including alkanolamine salts, such as diethanolamine hydrochloride, from about 1 to about 10% are most useful, while with respect to salts such as magnesium chloride amounts of from between'about 5 and 25% have beensuccessfully employed. In addition to magnesium chloride, zinc nitrate, aluminum chloride and other known conventional metal salts are normally employed in amounts corresponding to between 5 and 25 based on the weight of solids.

Following the application of the agent and curing catalyst to the textile fabric, the material is subject to drying and curingoperations in order to eifec't Wrinkle resistance and shrinkage control thereon. The drying and curing operation may be carried out in a single step or in separate steps. The temperatures at which the drying and curing operations are eifected vary widely and are influenced to some extent by the type of catalyst employed. Normally, the range of temperature extends from about F. to about 450 F. or even higher.' Generally speaking, the time of the drying and/or curing operation is inversely proportional to the temperatures employed and of course is influenced by whether or not separate or combined drying and curing steps are employed. Generally, when drying and curing is carried out in a cot bined operation a time of from about one minute to about 10 minutes may be employed at temperatures from 450 to- 250 F., respectively. When the fabric has been dried preliminary to curing, curing times of the order of 5 minutes to about /4 minute at a temperature of from between 250 and 450 F., respectively, have been successfully employed.

In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

- E01" convenience, resins referred to hereinafter as A through F correspond as set forth below to the following materials:

Resin Code Nomenclature l,3-dimethyl-4,5-dimethoxy-2-imidazolidinone.

dimethylol ethylene urea.

bis(methoxymethyl) urea.

bis(methoxymethyl) uron. 1,fi-din1ethylol3-(Z-hydroxyethyl) tetrahydrotriazone.

Equimolar blend of dimethylol ethylene urea and hexekis- (methoxymethyl) melamine.

EXAMPLE 1 No. Parts Parts Other Resin A Resin 1 11. 8 2. 11. 8 B 3 7.1 4.7 B 4 11.8 G 5- 7.1 4.7 C 0. 11. 8 E 7 7.1 4. 7 E R 11.8 F 9 7.1 4.7 F

The prepared solutions numbered 1 through 11 were applied to unmercerized 80 x 80 cotton percale by padding 36 x 16 inch swatches through a two roll micro-set padder approximating 85% wet pick-up on the fabric, equal to 5% resin solids on the weight of the fabric (owi).

All of the treated fabrics were dried for two minutes at 225 F. and then cured for one and one-half minutes at 350 F.

Wrinkle recovery tests were performed initially on the Monsanto wrinkle recovery tester in accordance with the Tentative Test Method 66-1959 of the American Association of Textile Chemists and Colorists. Results are shown in Table I.

Scorched tensile strength tests were performed initially and also after five sodium hypochlorite washes in accordance with the American Association of Textile Chemists and Colorists Tentative Test Method 92-1958. Results are also shown in Table I.

Table l RESIN BLENDS WITH 1,3-DIMETHYL-4,5-DIMETHOXY-2- IMIDAZOLIDINONE Monsanto Scott Tensile (lbs. Percent (owl) Wrinkle W+I") After 5 washes 1 Solution Solids Other Recovery Resin Resins (Degrees A W+F Initial 012 Percent Initial Scorch Scorch Loss 5 222 64 60 (l 5% B 208 51 21 59 3 2% B 256 69 60 C 255 19 0 100 3 2% O 241 54 36 33 5% E 259 46 31 33 3 2% E 242 51 49 4 5% F 269 45 29 36 9 3 2% F 257 56 47 16 Untreated" 152 87 87 0 AATCC-Tentative Test Method 92-1958-Pages 130, 131-1959 Yearbook.

6 EXAMPLE 2 A series of applications were made in which wrinkle recovery was determined as in Example 1 above by applying to cotton percale 5% solids on the weight of the fabric of 1,3-dimethyl-4,5-dimethoxy-2imidazolidinone (resin A) and a similar application was made so as to apply 5% solids on the weight of the fabric of resins B through F, identified above. These two points, representing the opposite extremes, namely of the resin solids being the compound of this invention on the one hand and 100% of the resin solids being an aminoplast on the other, were then recorded on a graph and the points connected with a straight line and indicating the expected bheavior of the resins based on various relative content of the two components in a blend being employed. Applications of blends both within and without the present invention in the same manner as the individual components were then made and tested for wrinkle recovery. It was determined that compositions within the contemplation of this invention produced points above the line of normal behavior on the aforesaid graph, establishing that a synergistic result had been obtained. A summary of this work appears in Table II hereinbelow, in which under Resin Designation reference is made to graphs 1 through 5, not here reproduced but referred to hereinabove.

Table 11 SUMMARY OF WRINKLE RECOVERY RESULTS [Results in degrees] Resin Percent Normal Expected Found Improve- Designation Solids Wrinkle Wrinkle Wrinkle ment By owf. Recovery Recovery Recovery synergism Graph #1:

COCO

5.0 222 5.0 269 3.0 F 2.0 241 257 16 Untreate 152 EXAMPLES A series of graphs similar to those referred to in Example 2 above were prepared to determine tensile strength losses after five chlorine bleaches and scorchings. Such values were plotted and again connected on a graph and again the points at the extremes in resin concentration were connected with a straight line, yielding the values for the expected behavior of mixtures of the two resins indicated based on the composition of the resin blend. As in Example 2, points obtained below the line indicate that less than expected loss in tensile strength is obtained with all combinations within the scope of this invention. The results of this work are demonstrated in Table 111 hereinbelow.

. 7 Table III SUM'MARY OF TENSILE STRENGTH LOSS AFTER CHLORINE BLEACHING AND SCGRGHING It will be apparent that various additives may be employed with the resin blends of, this invention without adverse effect on its performance on the treated textile material. Thus, additional thermosetting resinous components may be employed as Well as various thermo-plastic textile finishing resinous compositions of the type normally employed to modify hand and the like. Thus, such additional materials may be employed as enhance softnesstullness, firmness, draping qualities, water repellency, fire retardance and the like, as well known to "those skilled in the art of textile finishing, without departing-from the spirit and scope of this invention.

1. A composition comprising a compound of the formula:

it R-N-GN-R1 R4 G B2 0B3 where X is a member selected from th group consisting of O and S, the Rs are selected from the group consisting ofhydrogen, methyl, ethyl, propyl and butyl and an iamin'oplast, said compound and said aminoplast being present in said composition in relative amounts by weight of from 4:1 to 1:4, respectively.

2. An aqueous solution comprising a compound of the formula:

R-N- C -NR1 R4- i I Rs OR: OR;

where X is a member selected from the group consisting of O and S, the Rs are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl and an aminoplast, said compound and said aminoplast being present in said solution in relative amounts by weight of from 4:1 to 1:4, respectively.

3. A method for finishing cellulose containing textile materials to impart wrinkle resistance with minimum loss in tensile strength which comprises applying thereto a composition comprising a compound of the formula:

8 where X is a member selected from the group consisting of O and S, the Rs are selected from the group consisting of hydrogen, methyl, ethyl, propyl and'butyl, an aminoplast and a curing accelerator for said compound and said aminoplast, and thereafter subjecting the material to heat to cure said composition to a water insoluble state, said compound and said aminoplast being present in said composition in relative amounts by Weight of from 4:1 to 1:4, respectively.

4. A method for finishing cellulose containing textile material which comprises applying thereto a composition comprising a compound of the formula:

where X is a member selected from the group consisting of O and S, the Rs are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl, an aminoplast and a curing accelerator for said compound and said aminoplast, said compoundand said aminoplast being applied in an amount of between 1% and 15% based on the dry weight'of the textile material and thereafter subjecting the material to heat to cure said composition to a water insoluble state, said compound and said aminoplast being present in said composition in relative amounts by weight of from 411 to 1:4, respectively.

5. Cellulose containing textile material characterized by Wrinkle resistance and minimum tensile strength loss when scorched subsequent to chlorine bleaching having thereon and cured to a'water insoluble state a composition comprising a compound of theformula:

where X is a member selected from the group consisting of O and S, the Rs are selected from the group consisting of'hydrogen, methyl, ethyl, propyl and butyl and an aminoplast, said compound and said aminoplast being present in said composition in relative amounts by weight of from 4:1 to 1:4, respectively.

'6. Cellulose containing textile material having thereon in a water insoluble state from' between about 1% and 15% based on the dry weight of the textile material of a compound having the formula:

R4C-(EB5 where X is a member selected from the group consisting of O and S, the Rs are selected from the group consisting of hydrogen, methyL'ethyl, propyl and butyl and an aminoplast, said compound and saidaminoplast being present in said composition in relative amounts by weight of from 4:1 to 1:4, respectively.

References Cited in the file of this patent UNITED STATES PATENTS 2,339,203 Stiegler et al. Jan". 11, 1944 2,602,018 Beer July 1, 1952 2,613,210 Hurwitz et al. Oct. 7, 1952 2,376,062 Torlce et a1. 7 Mar. 3, 1959

Claims

3. A METHOD FOR FINISHING CELLULOSE CONTAINING TEXTILE MATERIAL TO IMPART WRINKLE RESISTANCE WITH MINIMUM LOSS IN TEXTILE STRENGTH WHICH COMPRISES APPLYING THERETO A COMPOSITION COMPRISING A COMPOUND OF THE FORMULA: