US3578592A - Imidazoline quaternary salts as soil retardants - Google Patents

Abstract

THE USE OF IMIDAZOLINIUM HALIDES AS SOIL RETARDANTS FOR NON-CELLULOSIC TEXTILE MATERIALS, THE TREATED TEXTILE MATERIALS AND A STABILIZED COMPOSITION CONTAINING SAID HALIDE AND A FORMALDEHYDE-BISULFITE ADDITION PRODUCT.

Description

United States Patent 3,578,592 IMIDAZOLINE QUATERNARY SALTS AS SOIL RETARDANTS Joseph John Pontelandolfo, Piscataway Township, Middlesex County, N.J., assignmto American Cyanamid Company, Stamford, Conn. No Drawing. Filed Oct. 3, 1967, Ser. No. 672,461 Int. Cl. D06m 13/40, 13/46 US. Cl. 2528.8 1 Claim ABSTRACT OF THE DISCLOSURE The use of imidazolinium halides as soil retardants for non-cellulosic textile materials, the treated textile materials and a stabilized composition containing said halide and a formaldehyde-bisulfite addition product.

R represents an alkyl group of from 15 to 21 carbon atoms and the X is a halide ion of the group consisting of chloride, bromide and iodide.

Currently, in the rug and carpet industry, widespread use is being made of fibers other than Wool in making carpet pile. Additionally, the carpets thus made are being offered in light or pastel colors. Such developments have given rise to an increased need for effective and longlasting soil retardants to justify the costly installation of such carpets, which are more readily soiled than wool carpets and, when light colored, more readily exhibit soiling.

Soil retardants heretofore used or suggested include colloidal dispersions of inorganic oxides, such as silica, alumina, titania, and the like. These inorganic colloids are useful to some degree but have short service life, especially when carpets treated therewith are vacuumed. The inorganic colloids also cause discoloration or whitening of the treated carpets so that an undesirable change in shade occurs even before the carpet is put into service use.

Certain other soil retardants of organic nature have been employed. This type also suffers from deficiencies including one or more of the following, depending on the specific organic variety: (1) not universally effective on carpets of all fiber types; (2) impart stiffness or rigidity to the carpet pile resulting in undesirable hand or lie of such pile and embrittlement thereof; (3) cause discoloration or whitening of the carpet leading to an "ice undesirable change in shade even before service use; (4) lack reasonable durability to service use and cleaning, particularly when vacuuming; (5) require uneconomical usage levels for effectiveness. There exists, therefore, a continuing and increasing need for soil retardants which are effective on carpets of all fiber types and which overcome the deficiencies of the prior art soil retardants.

An object of the invention is to provide compositions of matter useful for imparting durable soil resistance or retardance to textile materials, particularly fiat or pile of all types, without causing discoloration or rigidity.

Another object of the invention is to provide a method for imparting durable soil retardance to textile materials such as fiat or pile carpets.

A further object of the invention is to provide soil retardant textiles, particularly carpets of all fiber types and color, Which also substantially retain their original coloration and hand, even after repeated vacuumings.

These and other objects, features and advantages of the invention are further detailed in the description which follows.

In copending, commonly assigned application, Ser. No. 668,178, filed Sept. 15, 1967, certain imidazolines, as the free base or as a salt of a lower alkanoic acid, have soil retardant properties. However, the soil retardancy with the free base and the stability of the concentrated aqueous compositions containing the salts are not as great as desired.

It has now been discovered that the imidazolinium halides of Formulas I and II can be used as durable soil retardants for non-cellulosic fibrous textile materials, and particularly for pile type fabrics such as rugs and carpets. It has also been discovered that concentrated, stable aqueous dispersions of the quaternary salts can be made by incorporating therein a formaldehyde-bisulfite stabilizing agent.

The imida'zolines, from which the imidazolinium salts of Formulas I and II are prepared, can be formed by reacting a fatty acid of from 12 to 22 carbon atoms with diethylenetriamine according to published procedures. The preferred starting imidazoline is 1-(2-stearoylaminoethyl)-2-heptadecylimidazoline, prepared from two moles of stearic acid and one mole of diethylenetriamine.

The imidazolinium halides of Formulas I and II are obtained by reacting the corresponding imidazoline with an alkylating agent that will provide the 2,3-dihydroxypropyl group and the halide anion X-. Suitable alkylating agents include the halohydrins, i.e., halo-propanediols, such as S-chloro-1,2-propanediol, 3-bron1o-1,2-propanediol, and 3-iodo-l,2-propanediol, and the epihalohydrins, such as epichlorohydrin, epibromohydrin and epiiodohydrin.

The reaction between the imidazolines and the alkylating agent is conveniently carried out in water at a temperature of -95 C. Although theoretically a minimum of one mole of alkylating agent is required per mole of imidazoline for imidazolinium halides of Formula I and two moles for imidazolinium halides of Formula II, it is advantageous to use an excess (up to three moles) to obtain maximum fluidity of product.

In Formula I, quaternization is shown on the l-nitrogen atom, but this does not preclude quaternization on the 3-nitrogen atom instead of the l-nitrogen atom.

The preferred quaternary salts are l-(2-stearoylaminoethyl) 2 heptadecyl l- (2,3-dihydroxyprop yl)imidazolinium chloride and 1 (2-stearoylaminoethyl)-2-heptadecyl 1,3 bis(2,3-dihydroxypropyl)imidazolinium dichloride, and mixtures thereof.

The imidazolinium salts (Formulas I and II) are conveniently applied to the textile materials as aqueous dispersions. The physical properties, including stability, homogeneity and fluidity, are improved by incorporating therein a formaldehyde-bisulfite addition product. Between 0.7% and 7.0%, preferably between 1.7% and 3.5%, based on the weight of the imidazoline, of the formaldehyde-bisul-fite addition product should be employed. Addition of the formaldehyde-bisulfite stabilizer to an equeous dispersion containing about by weight of the imidazolinium halides changes the composition from a paste to a fluid.

The stabilized aqueous compositions containing the imidazolinium halides of Formulas I and II are applied to fibrous textile materials, either to the finished goods or during manufacture thereof, by any suitable means such as dipping, padding, spraying, coating, and the like. For application to carpets, spraying is the preferred technique, although mechanical applicators may be used on previously installed carpeting. The amount of solids of the composition applied to the fibrous material is not critical and may vary from about 0.1 to about 10.0%, based on the weight of fibrous material. Preferably, the amount of solids applied to carpet pile will be between 0.5 and 5.0% based on the weight of the pile. The treating composition should contain sufiicient solids to deposit the required amount on the fibrous material by the particular application method employed.

After the treating composition has been applied, the fibrous material is allowed to dry so as to remove the water. Drying may be accomplished at ambient conditions or, where possible, at elevated temperatures. The use of an oven circulating hot air at about 140 F. has been found particularly advantageous. The time required for drying in such ovens will depend on the temperature of the oven and the amount of water in the carpet pile.

Compositions of this invention are effective on noncellulosic fibers of all types, natural and synthetic, singly or in blends. Of particular interest are the synthetic fibers, such as nylon, acrylics, polyesters, and the like. Preferably, the fibers are in the form of a carpet with loop or cut pile. Such carpets may contain a backing material, for example, burlap, and the backing material may be treated with resins or rubber, etc.

EXAMPLE 1 This example shows the preparation of an imidazoline of the following formula:

A solution of 1,704 parts (6.0 moles) of stearic acid in about 1,050 parts of xylene was prepared by melting the stearic acid and adding the xylene. To this solution 310 parts (3.0 moles) of diethylenetriamine was added slowly while keeping the temperature below 90 C. The mixture was then heated at 110-115 C. under sufiiicent vacuum to cause azeotropic distillation of the water of reaction. The last amount of water was removed at a temperature of about 120 C. The xylene was then distilled and the residue was dried. The product was the desired 1-(Z-stearoylaminoethyl) 2 heptadecylimidazoline, shown above.

4 EXAMPLE 2 This example shows preparation of mixed quaternary salts of an imidazoline of the following formulas:

EXAMPLE 3 An aqueous dispersion containing 2.8% of solids was prepared by mixing 13.3 parts of the product of Example 2 with sufiicient water to make 100 parts. The dispersion *was applied by spraying to a 12" x 12" carpet sample consisting of cut nylon pile and 50% burlap backing. Spraying was confined to the pile and the carpet sample increased 50% in weight. Since the carpet increased in Weight by 50% and contained 50% pile to which the spray was directed, it may be concluded that the pile actually increased in weight by 100% and thus the pile contained solids equal to the concentration of the application hath, that is, 2.8%. The treated carpet was dried in an oven circulating hot air at C. After drying, the carpet was vacuumed to remove loose pile and incidental dirt.

Soiling tests were then conducted by placing the carpet along with untreated carpets on the floor in a special pattern. Carpets were exposed to foot traffic, e.g., dry soil, Wet soil, tarry deposits, and the like. The design of the samples was changed periodically according to a plan similar to that proposed by the American Association of Textile Chemists and Colorists, American Dyestuif Re porter, May 13, 1963, pages 56-93.

After each pattern change, the recommendations were followed to a predetermined level of soiling and including vacuuming. Reflectance measurements were made on the carpets before and after exposure to soiling, and the soil index values calculated as described in Accelerated Soiling Test-Iuvenon Soil Retardant R, Textile Finishing Bulletin No. 148A, American Cyanamid Company, Bound Brook, N.J., December 1955.

The results are shown in Table I.

TABLE I Treatment: Soil index None 1.00 Product of Example 2 0.54

Values of soil index below 1.00 indicate retardancy and the lower the said value, the more favorable is the soil retardancy. The untreated control in a soiling test is arbitrarily defined as having a soil index of 1.00 and performance of other samples is calculated on this basis. Good soil retarders generally have a value below about 0.70.

The results of this example show the high soil retardancy obtained when quaternary salts of Formulas I and II are applied to pile carpets.

5 EXAMPLE 4 TABLE III In this example, a series of aqueous compositions of Treatment: Soil index various salts of the product of Example I were prepared. None 1.00 The proportions of materials used are shown in Table II. Product of Example 4a 0.59 The compositions were examined for physical appearance 5 Product of Example 4b 0.55 as noted inTable II. Product of Example 5 0.72

TABLE II Imidaz- Salt Stabioline former lizer Water Dispersion parts Salt former agent parts parts parts appearance Example Number:

9. 15 Epichlorohydrin 6 1.0 76 Fluid.

15 .do 10 1.0 74 Paste.

20 12 1.3 67 Thick paste.

15 Dunethyl sulfate 7 1. 77 Lumpy.

l 0 1.0 74 Precipitate.

16 H01 (concentrate) 4 1.0 79 Solid.

H3504 (concentrate), 5 1.0 78 Precipitate.

15 HsPOe (85%) 11 1.0 73 Thick paste.

This example demonstrates several things. The use of a larger amount of epichlorohydrin results in a thick paste rather than a fluid dispersion. The well known quaternizing agent, dimethyl sulfate, cannot be used in this invention. The salts obtained with the common mineral acids do not provide stable, fluid compositions.

EXAMPLE 5 A concentrated aqueous dispersion of the product of Example 1 was prepared by vigorously mixing 300 parts of the product of Example 1 into 1200 parts of Water containing 60 parts of a cationic surface active agent obtained by reacting a long-chain alkyl amine with ethylene oxide.

EXAMPLE 6 Three aqueous dispersions containing 2% of active solids were prepared from the products of Examples 4a, 4b and 5. The dispersions were applied to nylon carpet by the procedure described in Example 3. The results are shown in Table III.

UNITED STATES PATENTS 2,874,074 2/ 1959 Johnson 2528.8 3,033,704 5/1962 Sherrill et al. 117-139.50 3,424,680 1/1969 Van Loo et a1. 2528.8

WILLIAM D. MARTIN, Primary Examiner J. E. MILLER, Assistant Examiner U.S. Cl. X.R. 1l7l39.5