US2982751A - Process and composition for rendering synthetic hydrophobic material antistatic and the product obtained therefrom - Google Patents

Description

United States Patent PROCESS COMPOSITION FOR RENDERING SYNTHETIC HYDROPHOBIC MATERIAL ANTI- AND THE PRODUCT OBTAINED THERE- Harrison I. Anthes, Waynesboro, Va., assignor to E. L

du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Nov. 17, 1958, Ser. No. 774,137'

7 14 Claims. (Cl. 260-291) This invention relates to new compositions ofmatter. More particularly it is concerned with a synthetic, hydrophobic shaped structure bearing a novel finish to minimize the accumulation of charges of static electricity during finishing operations andnormal use.

One common disadvantage of synthetic, hydrophobic shaped structures such as foams, fibers, filaments, yarns, staple, fabric, pelliclesand the like, is that they tend to develop static electrical charges. This feature is objectionable during the manufacture of textiles and in the finished garment. During manufacturing, static charge from the fibers or fabric interferes with convenient han- 'and Patented May 2, 1961 ice -R is not critical provided it is inert to reaction with amines, 'it may be any member of the class consisting of wherein A is a .member of the class consisting of divalent aliphatic, alicyclic, aromatic and heterocyclic radicals. Preferably -A. is hydrocarbon. A particularly desirable class of polyamines are those of the formula? H [-XCH CH (OCH CH q OCH CH ],,XH (11) wherein -X- is a member of the class consisting of N-YN R l wherein --R' is a member of the class consisting of 1 hydrogen, lower alkyl (i.e., "an alkyl radical containing dling during spinning, reeling, weaving, and the like operless thanabout 8 carbon atoms in its longest chain) and amino lower alkyl and Y- is divalent aliphatic which while it may contain aza linkages is otherwise hydrocarbon, q being a number from about 6 to about 40. The preparation of these poly-amines is discussed in detailrin Belgian Patents 554,506, grantedlanuary 25, 1 957 and 560,446, granted September 14, 1957 In general, the polyethylene glycol dihalide (e.g'. chloride, bromide or iodide) analogue is condensed v(with release of hydrogen halide) with an amine, the nitrogen of which contains at least two active hydrogen. Typical of such amines are methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, dodecylamine, 'allylamine, monoethanolamine, 3-isopropyl-n-propylamine, S-methoxy-npropylamine, d-iethylenetriamine, ,bis(3 aminopropyl)- other common yarn-treating agents which are not stable in that pH range, making it necessary to apply the agent in a treatment step distinct from that employed for other purposes.

It is an object of the present invention to provide a v composition which will impart durable antistatic protection to a synthetic, hydrophobic shaped structure without causing objectionable changes in other properties.

It is another object to provide a water-soluble antistatic composition which is compatible with pH sensitive yarnfinishing ingredients.

A further object is to provide a treated synthetic, hydrophobic shaped structure which minimizes or eliminates build-up of electrostatic charge and otherwise possesses substantially the same properties as the same structure before treatment.

Another object is to provide a process for imparting durable antistatic properties to a synthetic, hydrophobic shaped structure.

These and other objects will become apparent in the course of the following specification and claims.

In accordance with the present invention a synthetic,

hydrophobic shaped structure which minimizes accumu-,

lation of charge of static electricity is provided by epoxide curing a synthetic, hydrophobic shaped structure bearing a polyamine of the formula:

. (CH CH O),,-CH CH ],,-XH (I) wherein R is a divalent radical, X-- is a member of the class consisting of amino nitrogen and divalent radical terminating in amino nitrogen, m and n are small whole numbers from about 3 to about 40 and p is aninteger no greater than about 10. Since the nature of amine, v bis(2-aminopropyl) amine, hexamethylene diamine, triethylene tetramine, tetraethylene pentamin'e and the like. ket, typical products corresponding in general to Example 10 of Belgian Patent 560,446 and Example 1 of Belgian Patent 554,506. Assignee of the Belgian patent, the Onyx Oil and Chemical Company of 115 Norris Street, Jersey City, NJ., markets such productsunder the trademarks Aston 108-and Aston LT.-:; Y r

By epoxide curing? is meant that the polyamine defined above is reacted, after application of the reactants to the said shaped structure, witha polyepoxide. Such materials can be prepared by condensing epichlorohydrin with a polyol. A typical example is the condensation product (with elimination of HCl) of glycerine and epichlorohydrin. Preparation of these products is'described in detail in British Patent 780,288, dated July 31, 1957. Such a material with a molecular weight of between about 280 and 360-is availableon the open market under the trademark Eponite 100 (viscosity 90-150 cp. at 25 C.; 10.2 lbs/gal.) by the Shell Chemical Corp. of 500 'Fifth Avenue, New York, N.Y. Other similar commercial products from the same source include the Epon resins whichare diepoxide condensation products of epichlorohydrinand dimethyl, di-para hydroxyphenyl methane and the poly(allyl glycidyl ethers). A typical siloxane is 1,3- bis-[-3-(2,3 epoxy propoxy) propyl]tetramethyldisiloxane sold under the trademark Syl-Kem 90 by Dow Corning Corp, Midland, Michigan. Reaction of the polyamine (I) or (II) with the polyepoxide may be conveniently accomplishedby heating the shaped structure to which the mixture of the amine and polyepoxide has been applied.

In the examples which follow, unless otherwise stated, the washed fabrics are washed in a Kenmore portable Such materials are available on the open marwasher at 140 F. using 0.125% Tide detergent in the presence of a small amount of trisodium hexametaphosphate, then thoroughly rinsed and dried. The dry cleaning operation employed involves a -minute tumble at room temperature using a solution of the followingrfabricin 100 times its'weight of bleaching bath containing:

.2% sodium chlorite .2% oxalic acid .11% nitric acid .5 sodium nitrate 99% water,

heatingto boiling, maintaining at boiling for 1 hour, and subsequently rinsing the fabric in 'warm water; The bleaching operation is then completed by'a scour, -i.e.. boiling the fabric forminutes in 100 times its weight of a detergent mixture consisting of-:- Y a are; made under controlled conditions of 25% relative urements are made using aPhoto'volt-Modl 610 're flec ness and yellowness' canbe estimated.

aw (yellowness factor) tometer. By using green, amber-,andblu'e filters,'g'ray where: B=Reflectance with blue filter fG=Refleotance with green filter The following examples are cited toillustrate the in- 3 ventio'n. They are not intended to limit itin any way. Unless otherwise noted, parts as expressed "in the examples indicates-parts by weight. EXAMPLE 1 100 parts of the polyamine formed by condensation of diethylene triamine .with the dichloride of polyethylene glycol having a molecular weight of 600 (Aston LT as identified above) as a 20% solids solution inwater is stirred, into 5000 parts of water. The pHof the resulting solution is adjusted to 3:2 by addition'of '70 parts of a 10% solution of hydrochloric acid in w'at'er. 62 parts of Eponite 100 as identified above is then added and the mixture is dispersed using a Waring 'Blen'dor. While mixing in the Waring Blendor, 4 parts of zinc fluoroborate catalyst as a 40% aqueous solution is added. A stable homogeneous emulsion is formed.

A swatch of tropical plain weave fabric woven from a polyethylene terephthalate yarn is dipped into the emulsion prepared as described above and squeezed between the rollers of a hand wringer. The fabric is then cured for 5 minutes in an oven, at. j160 C. and thereafter scoured for 15 minutes at F. The fabricis 0bse'rved'to have gained 3.2% by weight of antistatic finish based on the original'weight of the fabric; 'Tlie treated fabric has a Log R of 10.3' compared Withan' original Log R of 14.2. After the standard bleaching the sam: plc is observed to have a Log R of 12.9. I a

A 21% by weight finish based on theweight of the fabric is attained when 1240 parts of' Eponite 100" is employfid using the technique described above. In this case 80 parts of the zinc fluoroborate catalyst is employed. The product has a Log R of 11.0 before the standard bleaching and a Log R of 11.5 after the bleaching,- EXAMPLE "2 Example 1 ismodified by employing as the 'polyarnine component the reaction product of the dichloride of polyethylene glycol having a molecularweight of 600 with methyl amine (Aston 108 as identified above); The percent by 'weight of finish picked upby' the fabric samples as well as LogRs before and after standard bleaching when using 62 parts of the diepoxide (A) and when using 1240 parts of the'diepoxid'elB) are shown inT-ableI.

Table I Sample Percent by wt. Before After -Bleach- Bleach A 2.8 -10.0 10.6 B --V----I 17 Sample (B) isfound to be waxy and still.

EXAMPLE 3 Table II- Sample Identity I G- Tropical plai'n'weave from polyethylenetere'phthalate yarn; D Twill fabric woven from a yarn produced from a polymer of acrylouitrilev (0rlon, a trade marked product produced by E. I. du Pont de Nemours and Co. -'of W11- mlngton, Del.). 7 E Trlcot fabric knittedwith a polyh'exainethy'lene-adipamide yarn. F Tafieta fabric woven from a polyhexamethylene-adipamide yarn. I

The finish is applied using -a laboratory-padder'set at 50 lbs. persquare inch providing two dips and twonips. After padding all. fabric samples are dried overnight at room temperature and thereafter cured for 6 minutes at C. Thein'itial L'o'g R of theisamples, the percent by weight of antistatic agent deposited "based on the weight of the fabric 'an'd'the Log Robservation's before and after washing, bleaching anddry cleaning are shown inTableIII.

padded upon four Table III Table V" 1v LogR Treated ,Fnishing 3011]. L R r ornpn. per LogR Amount 1,000 cc. H 0) 3 Sample (Un- Antlstat After 7: Hrs; treated) (Percent Washing. 1 1Dry Sample f WF Bleach Clean. fEpon" Poly- Bdry dry 1 Resin amine l'wash 5 10 claim clean- ,0 5 r 23 -562 (parts) I washes washes ings ings 14.2 0 9 11.2 10.9 10.9 10.8 12.7 16;3 2 5 10.3 10.6 10.2 10.5 12.6 0 l0 14.6 16.3 1 1 11.9 12.1 ,12.3 11.9 13.6 2.5 10 10.9 1 2 11.7 12. 7 12.6 11.3 13.2 6.2 10 10.7 Y 12.3 10 10.4 g 12.3 0 14.6 For comparauve purposes swatches of sample fabrics 0 0 C, D and E above are padded with a solution containing 106 parts of water, 175 parts of an aqueous solution containing 35 parts Aston 108 and 17 parts of a 90% aqueous solution of the diiodide of polyethylene glycol having a molecular weight of 600. ThepI-I is adjusted with sodium hydroxide to 11.1. After drying at 212 F. fabrics are cured for about 3 minutes at 300 F. and thereafter scoured. The amount of finish pickup and the Log R before and after and combination of one bleach and one scour are shown in Table IV. Comparative figures for similar samples treated in accordance with the present invention are included in the table. The samples treated with the finish cross-linked with the diiodide are labeled C1, D and E In addition the table shows a comparative figure of yellowness factor relative to samples C and C D and D These compare to the A cationic blue tint when added to the compositions. employed in treating. samples H, I and .1 results in re-v duction of the color of the samples to less than that of the control. In a similar manneroptical whiteners and silicone water proofing agents and other commonly used Examples 1 and 2 are: modified by employing as: the curing agent 62 parts of Syl-Kem 90 as identified above. The Log R of the samples M "and N respectively before scouring, after scouring and after 5 hours wash are reported in Table VI. I

yellowness factor of the untreated controls of 2.02 and Table VI 5.8 respectively. 1

, Table IV r LogR Pickup, Sample Percent Log R OWF Before After 5 hrs. Amount Scour Scour Wash Sample Antistat.

(Percent 1 Bleach Yellow- OWF) Initial 1 Scour ness M 2.9 10.9 10.5 12.5 Factor N 3. 1 10. 5 10. 2 12. 8

0.9 11.2 10.6 4.07 40 EXAMPLE 6 2.4 11.4 13.5 9.87 V a I V 1 212 8:? 121% if; A polyepoxide resin is preparedby mixing 15 parts 1.1 11.9 12.4 of sodium styrene sulfonate, 80 parts of diionized water, 2 0.15 part of glyceryl monooleate, .08- part of alkyl' phenoxy polyoxyethanol and 1 .67- parts of glycidyl EXAMPLE 4 methacrylate in a Waring Blendor to; form anemulsion.

epichlorhydrin and glycerine containing 2 epoxy groups per molecule. To serve as control solutions, Epon Resin 562 is omitted from one solution of polyethylene glycol amine, and' similarly, a 1% solution of Epon Resin 5 62 is prepared, omitting the poly-amine. All solutions are acidified to pH 2.5 with HCl, including apure water control containing no other ingredients. Samples of a tow of continuous filaments formed from a polymer of acrylonitrile (i.e. Orlon as identified above) are dipped into the test solutions at room temperature, wrung out to a solution pick-up of 100% and cured in a drying oven at 270 F. for ten minutes. The cured tow is converted into staple pads suitable for washing and testing for antistatic properties.

In this example in determining the durability of the antistatic-properties, washing tests are carried out with 0.1% aqueous Tide using a 15-minute wash cycle at The emulsion is added: to a 200 ml. 3-necked. flask which is then flushed with nitrogen. .06 part of a,a'aZ0biSiS0 butyryl nitrile is then added and the reaction mass is heated for 3 hours at 70 C. A thick semitransparent emulsion is formed.

05 part of the polyamine, Aston 108, ismixed. with? 1 Washing i 10.7 5 washings 12.1 10 washings 13.4

EXAMPLE 7' The technique of Example 4. is. followed in preparing; three antistatic finish reactants (M, N and 0) containing, the polyamine and diepoxide resin in a 1:1 weight ratio. Aston LT is employed as the polyamine in each applica-- tion. The emulsions are applied to a fabric. woven from a polymer of acrylonitrile (i.e.- Orlon as identified:- above) having an initial b; of 3.0. Theidentity of the diepoxide curing agent employed in each example is identified in Table- VII The color and ILog R ofeach sample after curing is reported inT'able Y 1 A diepoxide condensation product of epichlorohydrin and dimethyl, (ll-para hydroxyphenyl methane.

Table VIII I Sample br, 1 Bleach fiWashes 10 Washes 1 Log B. after one wash is 12.6.

EXAMPLE 8 A mixture of 50 parts'of Aston 108 (20% active ingredients), 10 parts Eponite 100 and 940 parts water is made up and adjusted to pH 3.5. A tow formed from a polymer of acrylonitrile (i.e. Orlon as identified above) is treated to provide a 100% by weight Wet pickup of this solution, then cut into staple and dried at 270 F. for ten minutes. 20 parts of this treated staple is then blended with 80 parts untreated staple and the blend is spun into yarn and woven into a twill fabric. Samples of the fabric are washed, tested, bleached, disperse dyed and basic dyed. All exhibit static protection after 10 washes as shown in Table IX.

Table IX Log R IJL Sample After 10 washes After 1 After 10 After wash washes dry cleanings g'reige fabric 4. 9 12. 5 l2. 7 13.7 bleached fabric 0. 7 12.6 13.0 disperse dyed fabrics l2. 8 13.3 basic dyed fabrics 12.6 12. 9 cotton. 13.3 wo 13. 7

wherein G and G are divalent hydrocarbon radicals. Typical polyamides and processes for their production are described in United States Patents Nos. 2,071,250; 2,071,253 and 2,130,948.

The term polymer of acrylonitrile is intended to include any polymer of acrylonitrile including polyacrylonitrile (i.e., the homopolymer) wherein the acrylonitrile component constitutes about 85% or more of the polymer molecule calculated as CH =CHCN. Many of the ethylenically unsaturated compounds which are suitable as the minor constituent in forming useful copolymers with acrylonitrile are listed in United States Patents Nos. 2,837,501; 2,486,241 and 2,436,926.

The polyesters from whichsuch structures may be devised include polyethylene terephthalate, polyethylene terephthalate copolyesters prepared using polyethylene glycols such as polyethylene vglycols having molecular weights of to about 6,000, or polyethers such as the dicarboxymethyl acid of polytetramethylene oxide or the esters polytetramethylene oxide, polydioxalane, or polyesters prepared using other acids such as bibenzoic, isophthalic or ethylene-bis-p-oxybenzoic acids. Such materials are described in United States Patent No. 2,465,319.

Application of the antistatic finish of the presentinvention may be made to any form of the shaped structure including foams, fabric, yarn, tow, staple, films, plastic sheeting and the like.

As described previously, the shaped structure is treated with an emulsion of a mixture of a polyepoxide and a compound of Formula I. Generally the emulsion is prepared by dispersing the polyamine and the polyepoxide in water at room temperature with vigorous stirring. The concentration of reactants in the emulsion-may vary widely. A concentration as high as 20% maybe used. However, more dilute emulsions containing from about 1 to about 5% of reactants are generally preferred. Any such finishing suspension having a concentration suitable to provide from about a 0.3% to about a 5% solids iokup based on the dry material is satisfactory. The reaction product can be applied to the structure by conventional methods such as dipping, padding, brushing, spraying, and the like. After removal of excess liquid, by wringing in the case of a textile, it is usually convenient to dry and cure the structure in one operation.

In forming the mixture of reactants the proportion of components may vary over a wide range. Preferably the ratio of polyarnine:polyepoxide is maintained within the limits of 10:3 to 10:7. Higher ratios of polyepoxide such as 1:1 may be used however, as illustrated in the examples. Larger amounts of the polyepoxide may be employed but generally result in a harsher hand.

While, as illustrated above, the reactants may be ap-- plied to the shaped structure without the presence of catalysts, it is preferred to include a minor amount of an epoxide curing catalyst. Such materials not only hasten the curing operation or permit curing at lower temperature, but also increase adherence of the antistatic agent to the structure. Such materials are well known in the art, as described, for instance in United States Patent No. 2,752,269. Although the reactant mixture may be either acidic or alkaline, alkaline conditions usually cause yellowing.

Optimum conditions of curing will depend upon the identity of the reactants, the identity of the textile and whether or not a catalyst is included. Room temperature is adequate for forming the cured antistatic finish when a catalyst is used. Generally, however, a temperature of at least about 240 F. is preferred to accomplish eflicient drying of the textile. Usually temperature adjustment is made to permit curing and drying in a 3- minute interval. A temperature of about 212 F. to 250 F. is recommended for most textile materials. For operation in the absence of a catalyst a curing cycle of about 10 minutes at 270 F. is adequate.

While applicant does not Wish to be-bound by any particular theory of mechanism, it is believed that the curing operation is accomplished by reaction of the epoxide with free hydrogen on the nitrogen of the polyamine. Thus it has been observed that fabrics treated with polyamines containing high proportions of active hydrogen (Aston LT) are stiffened to a greater extent upon curing than those where the polyamine has less tree hydrogen (Aston 108).

Many modifications of the above will be obvious to those skilled in the art without a departure from the inventive concept.

What is claimed is:

1. A composition suitable for minimizing the accumula- 9 tion of charge of static electricity of a hydrophobic shaped structure comprising a mixture of a polyepoxide and a polyamine of the formula:

H [XCH CH -(OCH CH -O CH CH- --X--H wherein X is a member of the class consisting of wherein R' is a member of the class consisting of hydrogen, lower alkyl and amino lower alkyl, -Y is a member of the class consisting of divalent aliphatic hydrocarbon and aza containing alkylene, q is a number from about 6 to about 40 and p is an integer no greater than about 10.

4. The composition of claim 3 wherein N- is N '10 5. The composition of claim 3 wherein the radical NYN it it is divalent diethylene triamine.

6. The composition of claim 1 wherein the polyepoxide is a reaction product of glycerin and epichlorohydrin.

7. A synthetic, hydrophobic textile bearing the reaction product of a polyepoxide and the polyamine of claim 1.

8. ,A synthetic, hydrophobic textile bearing the reaction product of a polyepoxide and the polyamine of claim 3.

9. The structure of claim 7 wherein the textile is in the form of a filament.

10. The structure of claim 7 wherein the textile is in I the form of a fabric.

11. The structure of claim 7 wherein the textile is formed from a polymer of acrylonitrile.

12. The structure of claim 7 wherein the textile is formed from a polyamide. I

13. The structure of claim 7 wherein the textile is formed from a polyester.

14. The structure of claim 7 wherein at least about 0.3% solids, based on'the dry material, of the epoxide cured polyamine is present upon the said hydrophobic textile.

References Cited in the file of this patent UNITED STATES PATENTS 2,772,248 Lieberman et al Nov. 27, 1956 2,794,754 Schroeder June 4, 1957 FOREIGN PATENTS 554,506 Belgium Ian. 25, 1957

Claims (1)

1. A COMPOSITION SUITABLE FOR MINIMIZING THE ACCUMULATION OF CHARGE OF STATIC ELECTRICITY OF A HYDROPHOBIC SHAPED STRUCTURE COMPRISING A MIXTURE OF A POLYEPOXIDE AND A POLYAMINE OF THE FORMULA: