US3595813A

US3595813A - Textile finishing compositions

Info

Publication number: US3595813A
Application number: US753079A
Authority: US
Inventors: Earl H Hartgrove Jr
Original assignee: JP Stevens and Co Inc
Current assignee: JP Stevens and Co Inc
Priority date: 1968-08-16
Filing date: 1968-08-16
Publication date: 1971-07-27
Anticipated expiration: 1988-07-27
Also published as: US3749597A

Abstract

A METHOD OF IMPARTING DURABLE ANTISTATIC FINISH TO HYDROPHOBIC MATERIALS NORMALLY SUSCEPTIBLE TO ACCUMULATING ELECTROSTATIC CHARGES COMPRISING TREATING SAID MATERIALS IN AN ACID ENVIRONMENT WITH A HYDROXY TERMINATED POLYFUNCTIONAL POLYOXYALKYLENE COMPOUND AND AN ACID-CATALYZED NITROGEN-CONTAINING CROSSLINKING AGENT.

Description

United "States Patent 3,595,813 TEXTILE FINISHING COMPOSITIONS lEarl H. Hartgrove, .lr., Parsippany, N.J., assignor to J. P. Stevens dz Co., Inc., New York, NY. N0 Drawing. Filed Aug. 16, 1968, Ser. No. 753,079 Int. Cl. (308g 23/14, 23/20, 25/00 US. Cl. 260-2 5 (Ilaims ABSTRACT OF THE DISCLOSURE lyzed nitrogen-containing crosslinking agent.

This invention relates to novel compositions used to finish hydrophobic substrates and to substrates produced therein.

More particularly, this invention concerns novel compositions used to impart durable antistatic finishes to hydrophobic textile materials which have a tendency to accumulate static charges.

The expression hydrophobic textile materials as used throughout this application refers to synthetic thermoplastics in the form of yarns, slivers, filaments, tows, fibers, articles and garments, and the like produced by drawing, spinning, combing, weaving, knitting or nonwoven procedures. Illustrative hydrophobic textile materials include the preferred polyesters and polyamides, the polyalkylenes such as polyethylene and polypropylene, polyacrylonitrile and the like, as Well as the mixtures of one or more of the hydrophobics and/or their blends with natural textiles such as wool and cotton. Rayon for the purposes of this invention is considered to be a natural textile since it is derived from a natural material, cellulose.

Textile materials manufactured from hydrophobic fibers, filaments, yarns, etc., have a relatively low capacity to retain moisture in comparison with their natural counterparts, cotton and wool, and normally tend to accumulate electrostatic charges in their processing during manufacture or during subsequent usage as a textile article or garment. For example, a garment manufactured from untreated hydrophobic materials will cling to the wearer rather than hang smoothly. In order to remove this objectional tendency or reduce it to acceptable levels, a great many antistatic finishes have been developed.

One of the most promising antistatic finishes which has been developed utilizes an alkaline-catalyzed interpolymer of a polyoxyalkylene compound with a polyfunctional amide and a quaternary ammonium salt described in copending Ser. No. 677,090, filed Oct. 23, 1967. This finish provides substantial reduction of the static charge of treated hydrophobic materials as compared to the untreated controls, is compatible with many common textile adjuvants, and is durable to repeated laundering. Unfortunately, the finish causes severe yellowing in white materials and off-shading in colored materials. This yellowing adversely affects the aesthetic appearance of the treated material and can place the finished materials at a competitive disadvantage compared to the same material before treatment. A comparable finish possessing all of the favorable characteristics of the aforementioned finish which does not cause yellowing would represent a substantial advance in the finishing of hydrophobic materials.

It is therefore an object of this: invention among others to provide durable antistatic finishes for hydrophobic materials, particularly polyester and polyamides and their blends with cotton.

Another object is the development of the above antistatic finish which substantially obviates the yellowing and shading problems of previous antistatic finishes.

Yet another object is the production of novel hydrophobic textile materials possessing good hand, durable antistatic properties without comprising the whiteness of undyed materials or the shading of dyed materials.

These objects and many others are attained by treating the hydrophobic substrates with a quantity of a curable antistatic finish, sufficient upon curing to impart an antistatic finish to the treated substrate, when processed according to the procedure described below.

More specifically, a hydrophobic substrate such as polyester, polyamide or the blends with cellulosics, is treated in acidic environment with:

(a) At least one nitrogen-containing polyfunctional polyalkylene,

(b) At least an acid-catalyzed nitrogen-containing crosslinking compound,

then the treated substrate is exposed to elevated temperatures to convert the resultant interpolymer to a Waterinsoluble film, having a reduced tendency to accumulate electrostatic charges.

In the preferred practice, a hydrophobic fabric or a blend such as polyester-cotton or polyamide-cotton is padded with an acidified aqueous formulation of (a) A polyhydroxy-polyglycolamine and (b) At least one acid-catalyzed nitrogen-containing agent,

then dried and cured between about to 200 C. for a sufiicient time to form a water-insoluble polymeric film upon the treated substrate and substantially reduce the specific area resistivity of the treated substrate compared to untreated controls.

In order to more easily acquaint the reader with the inventive concept, the following additional description is submitted:

(1) Application conditions The treating compositions can be in a variety of forms such as solutions, dispersions, emulsions, suspensions and the like. While aqueous formulations are frequently employed, non-aqueous formulations or mixtures of water with various solvents can be used. No particular mode of application is required. Any of the application methods used in the textile industry to treat textile articles are satisfactory. These include padding, dipping, sprarying, coating among others. The temperature of application is not critical to success and temperatures ranging from room temperature and below up to the boiling point of the solvent system can be employed if desired. The concentration of reagents in the treating solutions can vary considerably depending upon the wet pickup of the substrate. The critical factor is the add-on gain in the dried substrate. Experience has shown that this add-on must be at least 1%, and usually 3% or more, based upon the dry weight of the substrate to impart a sub- 3 stantial reduction in the tendency of the treated, cured substrate to accumulate electrostatic charges. This quantity of add-on is referred to as an antistatic imparting amount of finish. Higher quantities of add-on while affording satisfactory reduction of electrostatic charges given even greater antistatic durability upon laundering, but tend to adversely affect the hand and add to the cost.

(II) Catalysts One or more acids or their salts of mixtures of acids and salts serve as satisfactory catalysts for the required catalysis of this invention. Carboxylic acids such as citric acid, and mineral acids such as hydrochloric acid in diluted concentrations can be utilized. Alternatively acidic metallic salts such as zinc nitrate and magnesium chloride can be used by themselves or in conjunction with the acids. No particular quantity of acid need be employed as long as the pH of the system is below 6.0, preferably between about 3.5 and 5.5.

(III) Acid-catalyzed nitrogen-containing crosslinking agents The acid-catalyzed crosslinking agents employed in this invention are nitrogen-containing resin precursors, particularly those capable of being insolubilized at acid pH values. These resin precursors include those characterized as aminoplast resin precursors, ureaformaldehyde type resins and the substituted cyclic triazines. Suitable groups of resin precursors include dimethylol and polymethylol derivatives of urea, ethylene-urea, propylene-urea, dihydroxIyethylene-urea, thiourea, dicyandiamide, guanidine, esters of carbamic acid, the methylolated aminotriazines and methylolated triazines as Well as their etherification products. The preferred crosslinking agents are 1,3 bis(hydroxymethyl) 2- imidazolidinone, also known as dimethylolethyleneurea, N N N tris(hydroxymethyl)-melamine, hexahydro- 1,3,5 tris(3 methoxypropionyl)-s-triazine, and mixtures of these agents.

('IV) Polyfunctional polyoxyalkylene compounds The preparations of these compounds are disclosed in US. Pats. 3,351,622 and 3,197,463, and have structures selected from the group consisting of I I 1 and polrymers having recurring units selected from the group consisting of The preferred polyoxyalkylenes are those characterized within Formulas 4 and 5. The following more specific structures represent the recurring units of polyoxyalkylenes used in this invention:

N(CH3CH20)12CH2CHg-' C3H0(O CHzOHgQzOH Recurring Unit of PHPA and \+ N(CH CH O) OH OH,--

0 11;;(0 CH CHQ OH Recurring Unit of PHPA Hydrochloride (V) Antistatic interpolyrners of this invention I As indicated earlier, the antistatic interpolyrners of this invention are prepared by exposing admixtures of polyoxyalkylene reactants such as PHPA, acid-catalyzed crosslinking agents such as hexahydro 1,3,5 tris(3- methoxypropionlyl)-s-triazine, 1,3 bis(hydroxymethyl)- 2-imidazolidinone, and N N N tris(hydroxymethyl) melamine, and acidic catalysts to elevated temperatures until insolubilization takes place. The following kinds of reactions are believed to occur during the formation of the insoluble products when PHPA or a suitable salt (as the hydrochloride) is cured with the above crosslinking agents:

(A) A condensation process in which molecules of methanol are eliminated as by-products by reaction between (l) methoxy groups of hexahydro-1,3,5-tris(3-methoxypropi0nyl)-striazine, and

(2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

As a result, PHPA (or PHPA salt) is cosslinked and converted into a so-called l t-dimensional or ladder polymer.

(B) A condensation process in which molecules of water are eliminated as by-products by reaction between (1) hydroxyl groups of 1,3-bis(hydroxymethyl)-2-imidazolidinone, and

(2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

The net result is an insoluble, infusible, nonlinear polymer.

(C) A condensation process in which molecules of water are eliminated as by-products by reaction between (1) hydroxyl groups of N ,N ,N -tris (hydroxymethyDmelamine and (2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

An insoluble complex polymer results.

(D) In addition to the crosslink reaction per se, complex polymers are believed to be formed which contain segments of recurring units resulting from self-condensation of resin precursor. That is, PHPA (which may be in neutralized or partially neutralized form) crosslinked by means of 1,3-bis(hydroxymethyl)-'2-imidazolidin0ne or tris(hydroxyrnethyl)melamine also may contain blocks or grafted segments of recurring units resulting from condensation polymerization of such reactive resin precursors.

(E) When more than one crosslinking reactant is used in the process, the resulting insolubilized product is believed to have crosslinks stemming from each kind of reactant. Furthermore, the resin precursor may be present in the PHPA-containing product as blocks or grafted seg ments of polycondensed recurring units.

(VI) Reaction conditions for polymerization and insolubilization of antistatic finish In order to obtain the desired antistatic finish and to assure its durability to laundering, the finish must be insolubilized by polymerization in an acid environment. Heating is preferred to accelerate the polymerization reaction. The polymerization reaction is usually carried out in the,

presence of the hydrophobic substrate by an in situ process. For example, in carrying out the reaction in the presence of a textile substrate, an uncured finish is applied to the substrate to be treated. As indicated earlier, the finish can be in any of several forms. Acidified aqueous solutions are generally preferred for this purpose, although acidification can be done at any time prior to curing. Padding is the preferred form of application. The treated textile substrate is dried preferably between 50 and 105 C. to a moisture content of from about 0.01 to 3.0% by weight moisture, then cured by exposure to elevated temperatures until an insoluble hygroscopic polymer coating is formed.

The temperature at which the polymerization and formation of the insoluble coating takes place can vary considerably according to the reactants, concentrations, pH and catalyst employed. Generally, however, temperatures between about 100-200 C. are preferred.

In order to further described this invention, the following illustrative examples are submitted. Preceding the examples is a description of the test methods employed in evaluating the finish:

(A) Evaluation Test Methods Laundering: Each laundering was at 60 C. in a household washing machine with a commercial synthetic detergent. The number of laundering-drying cycles (none, 10, 20, etc.) is indicated by No. L, L, L, respectively, in the tables.

Specific Area Resistivity (SAR): Technical Manual of the American Association of Textile Chemists and Colorists, volume 35, pages 138-139 (1959), Electrical Resistivity of Fabrics, Standard Test Method AATCC 76- 1959. The relative humidity was unless otherwise stated. Fabrics having electrical resistivity values greater than 1X 10 ohms. are not satisfactorily antistatic, whereas the smaller the value is in comparison with 10 ohms, the more effectively antistatic the fabric is.

Parts and percentages were by weight, unless otherwise note Whiteness (with respect to yellowing), was observed on a subjective comparative basis and rated on a scale of 1 (white) to 25 (severest yellowing, as that resulting from the use of an alkaline catalyst). Whiteness ratings of 1 to 10 were acceptable, with scores of 1 to 5 being best.

(B) ILLUSTRATIVE EXAMPLES EXAMPLE 1 Acid-catalyzed antistatic finish for white nylon tricot based on polyhydroxy-polyglycolamine (PHPA) with hexahydro 1,3,5 tris( 3 methoxypropionyl) s triazine (TMPT) Weighed rectangular portions of white nylon tricot fabric were padded with appropriate aqueous solutions so percentages (on the weight of the fabric) resulted as shown in the following table.

The polyhydroxy-polyglycolamine had been synthesized from (1) the alkanolamine having the structure shown in the following equation, and

(2) a polyoxyethylene dichloride having the average composition shown:

Polyhydroxy-polyglycolarnine Before PHPA was used in the pad bath, enough S-normal hydrochloric acid was added to the PHPA to lower the pH to 5, in order to insure compatibility.

In the table, TMPT means hexahydro-l,3,5-tris(3-methoxypropionyl)-s-triazine, and Arquad 12-50 refers to a 50% aqueous solution of dodecyl-trimethyl-ammonium chloride marketed by Armour Industrial Chemical Company.

After the padding step, the treated fabric samples were dried and heated in a forced-draft oven for 3 minutes at approximately C. to bring about formation of an insoluble hygroscopic finish. A whiteness rating was made on each sample prior to washing and also after each sample had been washed in aqueous solution of 0.1% Triton X- 100, the trade name of Rohm & Haas Co., for the nonionic wetting agent which is the reaction product of p-( 1,1, 3,3-tetramethylbutyl)phenol and 9 to 10 mole parts of ethylene oxide, on the average.

The nylon fabric so treated had excellent appearance and durable antistatic properties.

In contrast to the excellent results obtained using an acid-type catalyst (magnesium chloride) with PHPA, TMPT, and Arquad on nylon tricot, results with respect to whiteness were completely unsatisfactory when the acidtype catalyst was replaced by an alkaline one (potassium carbonate). The comparative data are in the accompany ing table. (NOTE: Pretreatment of PHPA by HCl was omitted when the alkaline catalyst was used.)

TABLE FOR EXAMPLE 1 Evaluation, whiteness rating After wash Before wash Arquad PHPA TMPT 12-50 Catalyst EXAMPLE 2 Variation of Example 1 in which A melamine-formaldehyde condensate (Aerotex Resin M-3) was used along with TMPT and PHPA A weighed rectangular portion of white nylon tricot fabric was padded from an aqueous bath so percentages resulted as follows:

PHPA: 6.4% on the weight of the fabric (OWF) TMPT: 0.5% OWF (abbreviations as in Example 1) MgCl 0.7% OWF M3: 0.5% OWF (M3 means Aerotex Resin M-3, a

melamine-formaldehyde condensate marketed by American Cyanamid Co.)

Specific area resistivity, ohms Nylon tricot sample No L 10 L 20 L 30 L9 Example 2 2. 0x10" 0. 9x10 1. 4x10 11 1. 6x10 Untreated control 10 10 13 EXAMPLE 3 Variation of Example 1 in which 1,3-bis (hydroxymethyh- Z-imidazolidinone (DMEU) was used along with TMPT and PHPA Weighed rectangular portions of white nylon tricot fabric were padded with appropriate aqueous solutions so 8 percentages resulted as shown in the accompanying table. was present also. The padded fabric was heated for 3 Before PHPA was used in the pad path, enough S-normal minutes at approximately 150 C. Upon evaluation, whitehydrochloric acid was added to lower the pH of the ness and antistatic properties were both good.

TABLE FOR EXAMPLE 5 Evaluation White Percent on the Weight of the fabric nylon White- Specific area resistivity, ohms tncot Aerotex .Arquad ness sample No. PHPA TMP'I resin M3 DMEU HCHO 12-50 Mg 01; rating No L 10 L 20 L 30 L 24 6. 4 0. 5 0. 5 0. 5 1. 2 0.7 2 1. 8X10 0.4)(10 3. l0 2. 8X10 25 6. 4 0. 5 0.5 0.5 0.5 1. 2 0.7 4 2. 0X10 0.8)( 2. 5X10" 0. 7X10" EXAMPLE 6 PHPA to 5. In the table, DMEU means 1,3-bis (hydroxymethyl)-2-imidazolidinone. 'Ihe padded fabric was heated g iggg g zg gggsj gg g gg i figg jgi fg for 3 minutes at approximately 150 C. whiteness and by crosslinked PHPA annstatlc propertles were both good A procedure similar to that used in Example 1 was fol- TABLE FOR EXAMPLE 3 Evaluation White Treatment, percent on the weight of the fabric nylon White- Specific area resistivity, ohms tricot Arquad ness sample N o. PHPA TMPT DMEU 1250 MgClz rating No L 10 L 20 L L 10 6. 4 0.5 0.5 1. 2 0. 7 1 1. 3X10 0. 7X10 1. 7X10 2. 0X10 11 6. 4 0. 5 0. 5 0 0. 7 9 1. 2X 10 1.0)(10 Not determined EXAMPLE 4 lowed in padding portions of white nylon tricot fabric.

S1rn11ar to Example 1, but wlth the melamme-formalde- Pad baths were prepared as follows:

fi gg fg ff i g f $111 M4) and DMEU 30 Individual IOU-gram portions of PHPA were acidified to a pH of 5 by means of the various acids listed in the Weighed rectangular portions of white nylon tricot accompanying table. Each individually acidified portion fabric were padded with appropriate aqueous solutions so of PHPA was used to formulate pad baths to which the percentages resulted as shown in the accompanying table. following ingredients were also added, so the final con- Procedurai details resembled those of Example 1 (incentration of each ingredient in grams per liter of aqueous cluding the comparison test with the alkaline catalyst), solution was that shown: except that a combination of melamine-formaldehyde condensate (Aerotex Resin M-3) and l,3-bis(hydroxymethyl)-2-imidazolidinone (DMEU) replaced TMPA. The ig padded fabric was heated for 3 minutes at approximately Ingredient Example- Grams/liter 150 C A t M-3 As in Example 1, nylon fabric having the acid-catalyzed pilfhgj f fgu 13 5 6 40.0 finish of PHPA and the combination of reactive products fg 6 SJ based on amino (or amido) compounds had excellent d fP t 1 1 Tra e name 0 rec er & Gamb e 00. for a complex reactive long- Whlteness and durable antlstatlc propertles Whereas the chaincationiedispersionformulatedasasoitenerforcellulosies andnylon.

alkaline-catalyzed finish was unsatisfactory in those re- 2 Registered trademark of Sandoz, Inc., 61 Van Dam Street, New spects' Details are in the accompanying table York, N.Y. 10013, for an optical bnghtener (a flourescent white dye).

TABLE FOR EXAMPLE 4 W1 Percent on the weight of the fabric Evaluation 1 nylog Aerotex White- Specific area resistivity, ohms tricot resin Arquad ness sample Ne. PHPA M-3 DMEU 12-50 Catalyst rating No L 10 L 20 L 30 L 6 4 0.5 0.5 1.2 0.7MgCl2 3 2. 3x10 25x10" 2.8 10 1. 8X10 e 4 0.5 0.5 0 0.7 MgClz 5 2. e 10 2. 5x10 2. 4 10 1. 1x10 e 4 0. 5 0.5 1.2 0.7 KzCOa 23 10 10 EXAMPLE 5 In order to eifect drying and curing, each sample was Similar to Example 1, with melamine-formaldehyde conheated at fOf 3 m es, subjected to high-temdensate (aerotex resin M3 and DMEU used in com- Pefatufe aglng fo 16 hours) in air. p evalbination with TMPT (along with PHPA, as usual) uation, all treated fabric samples proved to be durably Weighed rectangular portions of white nylon tricot 65 antistatic. Sample 2, in which phosphoric acid had been fabric were padded with appropriate aqueous solutions to used as the acldlfylng agent, g the least disCOlOratlon yield the add-on percentages shown in the accompanyand even that very small degree of discoloration was ing table. Procedural details resembled those of Example li i ated by washing. Citric acid (Sample 6) resulted in except thatt a of three Teactlve Products very good whiteness, and hydrochloric acid (Sample 1) pased on aimmo (or amldo) compounds had been used resulted in good whiteness. But strong acids exerting a Instead of Just TMPA' dehydrating or oxidizing action resulted in discoloration h 5- 5 igxi ggi gs g s ig ggg gg ggg gl gi g to an undeslrable degree (sulfuric acid and n1tr1c acid,

PHPA to 5. In addition to PHPA and the three amino Samples 3 and respectively). Hence, e H inresin precursors in the pad bath, 0.5% of formaldehyde organic or organic acids may be used in this invention,

strong dehydrating or oxidizing acids are to be avoided. Among organic acids, those of low volatility are preferred TABLE FOR EXAMPLE 6 Evaluation after curing (135 C. for 3 minutes) and aging (100 C. for 16 hours) White nylon Acid for Specific area resistivity, ohms tricot acidifying sample the PHPA whiteness No L 10 L 20 L 30 L 1 Hydrochlorio Good 0. 5X10 2. 5X10" 3. 5X10" 1. 4X10" 2 Snlfuric 0.4)(10 1.4X10 0.9)(10 0.4)(10 3 Nitric 1. 3X10 1. 4X10 1. 4X10 1. 0X10 0. 7X10 1. 3X 10 2. X10" 1. (3x10 1. 9X10" 1. 1X 1. 4X10 1. 9x10 XAMPLE 7 EXAMPLE 9 Comparison of acid-type and base-type catalysts as to durability of antistatic finishes for nylon based on crosslinked PHPA A procedure similar to that used in Example 1 was followed in padding two kinds of tricot fabric knitted from Nylon 6. Samples of one series (designated by T appended to the sample number) used a texturized fabric made of pre-crimped fibers, whereas the other series of samples (identified :with the suffix U for untexturized) were made from fibers which had not been precrimped. Weighed rectangular portions of each kind of nylon fabric were padded with the appropriate aqueous solutions so as to effect the add-on percentages (based on the weight of the fabric) shown in the following table.

Similar to Example 7, but on W001 fabric TABLE FOR EXAMPLE 7 Add-on (in percent) based on the weight of the fabric Nylon Specific area Acrotex tricot resistivity, ohms Arquad resin sample Add-on formula N0. PHPA TMPI K 00 12-5o M-3 DMEU MgCh No. 5 L 15 L 71-T 3.4Xl0 10 6.4 0.8 0. 7 1.2 o 0 0 5% x10 1 101, 7 1.0x10 .0 10 6. 4 0 o 1. 2 0. 5 0. 5 o. 2 {7245 12x10? uxmw 0 {33 iififi 74-1 6.6 10 s.0 10 s. 4 0 u 0 0. 5 0. s 0. 2 8. 4X10 4 0x101 Control: Unpadded {T nylon tricot. U

NorE.T=Texturized; U= Untexturizcd.

In order to effect drying and curing, each padded sample was heated at 135 C. for 3 minutes. The treated sam- TABLE FOR EXAMPLE 9 ples and controls were evaluated for antistatic activity Adm specific area after 5 and 15 launderings, respectively, as measured by g reslstlvlty, Ohms specific area resistivity. g gz i e 5 L 15 L Whenever potassium carbonate (a base-type catalyst) 2 8X10 10 had been used in the formula added to the nylon, the regjgxm 10 28x10 suiting finish was not nearly so durably antistatic as when 5.7 10 10 13 a. 4x10 in 1. 0x10 12 magnesium chloride (an acid-type catalyst) was used. This can be seen by the data above in the accompany- 23x10 10 ing table.

EXAMPLE 8 Similar to Example 7, but on 100% polyester taffeta EXAMPLE 10 Similar to Example 9, but on worsted fabric The same kind of durability comparison between acid type and base-type catalysts demonstrated in Example 9 was carried out on worsted fabric which had been dimensionally stabilized through chemical modification by a reactive polymer having terminal aziridine rings. Addon was as those tabulated in Example 9. The suflix X identifies the worsted fabric samples. Drying-curing was effected by heating each padded sample at C. for 3 minutes. Again the acid-catalyzed finish was shown to be more durable than the base-catalyzed finishes.

TABLE FOR EXAMPLE l0 Add on Polyester Add-0n Formula taffeta Specific area resistivity, ohms Formula Worsted Specific area resistivity, 0111115 No. from sample No. from fabno Example 7 No. 5 L 15 L 20 L 70 Example 7 sample N0. 10 L 20 L 25 L 4. 10 10 71 71-X 4. 5X10 1. 0X10 13 10 13 7. 5x10 1.7)(10 72 72-X 3. 1X10 13. X10 2X10 73-. 73-X 3. 3X10 12 10 4, 5X10 7. 2x10 74-... 74-X 2. 7X10 1. 5X10 2X10 Control: Control:

Unpadded 10 13 Unpadded 10 15 EXAMPLE 1 1 Similar to Example G, but on a blend of polyester (55%) and Wool (45% by Weight) The comparison between acid-type and base-type catalysts illustrated by Example 7 Was carried out on a fabric made from a blend of polyester (55%) and wool (45% by weight). Add-on was as tabulated in Example 7. The suffix Y identifies the polyester-Wool fabric samples. Drying-curing was effected by heating each padded sample at 135 C. for 3 minutes. Data again indicated that more durable antistatic activity resulted from acid-catalyzed finishes than from base-catalyzed finishes.

TABLE FOR EXAMPLE 11 Formula Polyester- Specific area resistivity, ohms No. from wool fabric Example 7 sample No. No. L 5 L 30 L 2. 8X10 5 1. 1X10 11 10 13 8. X10 7 6. 8X10 9 3. 2X10 9 8. 0X10 3 1. 4X10 11 10 13 7. 5X10 B 6. 3X10 9 4. 8X10 Unpadded 4. 1X10 2. 4X10 11 13 EXAMPLE 12 Similar to Example 7, but on a blend of orlon (70% and wool (30% by Weight) TABLE FOR EXAMPLE 12 Acrylic- Add-on for- Specific area resistivity, ohms mula N0. from wool fabric Example 7 sample No. No L 5 L L 3.0)(10 2.9)(10 10 3.5)(10 5.3 10 2.7X10 4.0X10 1.4)(10 10 3.1X10 5.7)(10 4.9)(10 Control:

Unpadded. 1.5 10 1.7 10 10 As the above examples and discussion indicate, numerous advantages accrue from the practice of this invention. For example, a more durable antistatic finish is provided which does not yellow or adversely affect shading as does the base-catalyzed systems of the prior art. In addition, unlike the antistatic finishes which utilize the insoluble epoxide crosslinking agents, the systems of this invention employ water-soluble nitrogencontaining crosslinking agents. As a result of this there is no need to prepare emulsions or suspensions of variable stability in order to apply the antistatic systems. As a consequence of employing nitrogen-containing crosslinking agents, shelf stability of the formulations is improved, variations in durability are minimized and simpler application and formulation techniques can be used.

Numerous changes and modifications can be made in this invention Without departing from the inventive concept. For example, reactants, reaction conditions and substrates can be varied without substantially affecting the desired result. The metes and bounds of this invention are best determined from the claims which follow.

What is claimed is:

1. An insoluble antistatic acid catalyzed interpolymer of a polyhydroxy-polyglycolamine compound selected from the group of compounds represented by the structural formulas:

and polymers having recurring units selected from the group consisting of:

wherein A is an anion, m is an integer from 3 to 50, inclusive, n is 2, 3, or 4, p is 2 or 3, and q is an integer from 2 to 20, inclusive; and acid catalyzed nitrogen containing crosslinking agents selected from the group consistin g of hexahydro- 1 ,3,5-tris (3 -methoxypropionyl) -stri azine, mixtures of hexahydro-1,3,5-tris(3-methoxypropionyl)-s-triazine with 1,3-bis(hydroxymethyl)-2-irnidazolidinone, and mixtures of hexahydro-1,3,5-tris(3- methoxypropionyl)-s-triazine with melamine-formaldehyde condensates.

2. The insoluble antistatic acid catalyzed interpolymers of claim 1 wherein the crosslinking agent is hexahydro- 1,3 ,5 -tris 3-methoxyprop ionyl -s-triazine.

3. The insoluble antistatic acid catalyzed interpolymers of claim 1 wherein the crosslinking agent is a mixture of a melamine-formaldehyde condensate and hexahydro-1,3 ,5 tris 3-methoxypropionyl -s-triazine.

4. The insoluble antistatic acid catalyzed interpolymers of claim 1 wherein the crosslinking agent is a mixture of l,3-bis(hydroxymethyl)-2-imidazolidinone and hexahydro-1,3 ,5 -tris 3-methoxypropionyl -s-triazine.

5. An insoluble acid catalyzed condensation polymer of a polyhydroxy-polyglycolamine compound selected from the group of compounds represented by the formulas:

and polymers having recurring units selected from the group consisting of:

wherein A" is an anion, m is an integer from 3 to 50, inclusive, n is 2, 3, or 4, p is 2 or 3, and q is an integer from 2 to 20, inclusive; and hexahydro-l,3,5-tris(3-methoxypropionyl) -s-triazine.

(References on following page) 13 14 References Cited 3,356,524 12/1967 Buell 260-29.4 Kilkschnek et a1. 8/1958 Cooke et a1. 260-294 FOREIGN PATENTS 11/1961 Pitts 117 139.5R 5 976,712 12/1964 Great Brltain 260 849 2/1962 Pretka 2602 5/1964 Baechtold 5 JOHN C. BLEUTGE, Prlmary Examlner 6/1966 Cohen 260-29.2N 11/1967 Tesoro 117139.5R 11/1967 Kida et a1. 260-294 10 8115.6, 116.3; 117138.8, 139.5; 26029.2, 29.4, 849