Antistatic fiber containing chain-extended tetrols based on diamines
limited Mates Patent [1 1 Wells et al.  
 [ Apr. 8, 1975 ANTlSTATlC FIBER CONTAINlNG CHAIN-EXTENDED TETROLS BASED ON DlAMlNES [75] Inventors: Rodney Lee Wells; Lamberto Crescentini, both of Chester, Va.  
 [73] Assignee: Allied Chemical Corporation, New  
 York, NY.  
 [22] Filed: May 10, 1974 [2i] Appl. No.: 468,771  
 Related U.S. Application Data [63] Continuation-impart of Ser. No. 341,194, March 14,  
 1973, abandoned.  
 [56] References Cited UNITED STATES PATENTS 12/1957 Beaver 260/459 R 11/197] Crovatt..,.  
 4/1972 Weedon 260/858 OTHER PUBLICATIONS Chemical Abstracts; Shima, Takeo et aL, Vol. 72, 1970. Chemical Abstracts; Crovatt, Lawrence, Vol. 72, I970.  
 Primary Examiner-Paul Lieberman Altorney, Agent, or Firm-Fred L. kelly [57] ABSTRACT It has been suggested that antistatic properties of tibers of polyamide could be improved by uniformly dispersing in the polyamide between about 1 percent and about 12 percent by weight of a predominantly branched, chain-extended propylene oxide-ethylene oxide copolymer based on a diamine. However, with incorporation of this antistatic additive in the polyamide, serious problems have been encountered in meltspinning due to the frequent occurrence of nubs or enlarged places in the extruded polyamide filament. it has now been found that the occurrence of said nubs in the antistatic polyamide fiber can be greatly reduced by dispersing in the polymer about 005 to 12 percent by weight, based on the weight of the antistatic agent, of a phenol compound represented by the formula:  
 HO C 4 OH where R is an alkyl hydrocarbon group containing less than nine carbon atoms and R is a tertiary alkyl group containing at least four but not more than 12 carbon atoms.  
 10 Claims, No Drawings ANTISTATIC FIBER CONTAINING CHAIN-EXTENDED TETROLS BASED ON DIAMI Es CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of our copending application Ser. No. 341.194. filed Mar. 14. 1973. now abandoned which is directed to an improvement upon the invention disclosed in U.S. application Ser. No. 294.941. filed Oct. 11. 1972. U.S. Application Ser. No. 294.971 is hereby incorporated by reference into this application.  
 BACKGROUND OF THE lNVENTlON This invention relates to a process for the meltspinning of a&#39; filamentary structure from a synthetic polyamide polymer. More particularly. it is concerned with an improved process for the formation of an improved antistatic filament. yarn or the like by meltspinning a synthetic linear fiber-forming polyamide.  
  it has been suggested that the utility of synthetic fibers could be increased and their properties. in particular their antistatic properties. could be improved if a polyalkylene ether of high molecular weight is included in the polymer. More specifically. it is disclosed in U.S. Pat. 3.475.898 to Magat and Sharkey to use poly(ethylene-propylene)ether glycols for this purpose. More recently. U.S. Patent 3.657.386 discloses that certain propylene oxide-ethylene oxide copolymers based on ethylene diamine are useful in preparation of an antistatic fiber of polyamide. it has also been suggested that the utility of synthetic fiber of polyamide could be increased by dispersing in the polyamide an antistatic compound which is a reaction product of:  
 I (5H3 cH H(OCH CI 1 (ocnc% CH3 v N-A-N moca ca (O CHCH where a. b, c. d. w. .v, v and z are each a whole number and A is a difunctional radical from a hydrocarbon con-- taining 1 to 13 carbon atoms. said tetrol compound having a molecular weight between about 4,000 and about 50.000 and at least one compound selected from the group consisting of diepoxides and compounds which yield the following divalent radicals:  
 where R is a difunctional radical from a hydrocarbon containing 1 to 30 carbon atoms. However, serious problems were encountered in melt-spinning due to the frequent occurrence of nubs&#34; in the fiber. The term nubs&#34; is conventionally applied and is used herein to mean enlarged sections of filament no more than several filament diameters in length. Nubs may be formed by a foreign. non-orientable substance which interferes with normal fiber stretch in a short section, resulting in an enlargement. Foreign substances which are believed to have contributed to nubs in the present instance include carbonized polymer from face of extruder die and spinnerette. and gels formed in the polymer. Gels appear to be the chief cause. i.e.. the nubs are probably created by non-orientable gel from cross-linked polymer. Thermal degradation of the polymer may be an important causative factor.  
  The reactions in thermal degradation of polyamides containing polyalkylene ether additives are not entirely understood. It is likely that thermal degradation produces a decomposition product which serves to form cross-links between amide groups and adjacent polymer chains. The decomposition reaction proceeds slowly. finally building up a three-dimensional network of molecules which may be called polymer gel and which eventually reaches the stage where it forms an infusible coating on the walls of the reactor and other equipment.  
  A serious difficulty which arises from the formation of this polymer gel on the interior walls is that from time to time pieces break off and get into the flowing polymer stream where they produce damage to the spinning equipment.  
  The greatest difficulty, however. is caused by polymer gel which has progressed to the three-dimensional structural stage. but which has not yet reached the stage of being infusible. This kind of polymer gel is readily carried with the stream of flowing polymer. Being still molten or at least softened. it passes through the pump and even through the filter medium to show up either as discontinuities or as viscosity differences in the spun filament. When these filaments are later cold drawn. these defects may cause breaks in the filaments )CH CHO) a (CH CH O) H \CH CHO) b (CH CH O) H which either cause the whole thread to break or else form nubs which go through to be counted as quality defects in the final yarns.  
 SUMMARY OF THE INVENTION It is an object of this invention to avoid the above difficulties by minimizing gel formations in the molten polyamide. Another object is to avoid accumulation of polymer gel on the walls of the reactor. in the pump. or in the filtering medium when melt-spinning the polyamide. A further object is to improve the uniformity and quality of filaments or fibers formed from the molten polymer. in particular to minimize nub formation in the filaments. Other objects will become apparent from the 3 4 9 9 H (OCH CH y (OCHCIT C /(CH CHO) a (CH CH O) H CH N-A-N CH I I 3 H(OCH CH (OCHC (CH CHO) (CH CH O) H where R is a difunctional radical from a hydrocarbon containing 1 to carbon atoms, by extruding the mo]- ten polymer through an orifice into a quenching medium and thereafter stretching the resulting filaments, the improvement comprising dissolving in the extrudate prior to extrusion about 0.5 to 12 percent by weight. preferably 1 to 6 percent. based on the weight of the antistatic compound, of a phenol compound of the formula:  
 where R is an alkyl hydrocarbon group containing less than nine carbon atoms. and R is a tertiary alkyl group of at least four carbon atoms but not more than twelve carbon atoms. Such compounds may be economically prepared and give excellent results in the present invention.  
  As stated above, the present invention is an improvement upon the invention disclosed in US. application Ser. No. 294,971 which relates to an improved antistatic fiber containing a novel antistatic compound. The novel antistatic compound is prepared by reacting a tetrol compound. as described above. with a chainextender compound. for example a diepoxide, a dicarboxylic acid or a diisocyanate, to form predominantly branched. chain-extended polymer having a melt viscosity of about 800 to 50,000 centipoises, preferably 1.500 to 25.000 centipoises, at 100C. Preferably, the ethylene oxide moiety makes up 10 to 90 percent of the molecular weight of the antistatic compound. The mol ratio of chain-extender compound to tetrol compound is preferably between about 0.7 and 1.0.  
  The phenol compounds useful in the present invention are known compounds and some are commercially available. The phenol compounds of the invention may be prepared in accordance with US. Pat. No. 2,818,945.  
  The tetrol compound which is chain-extended for use as an antistatic additive in this invention is fully described in US. Pat. No. 2,979,528 to Lundsted, assignor to Wyandotte. These tetrol compounds are commercially available as Tetronic series block copolymers having molecular weights between 1,650 and over 26,000. This series varies in length of poly(oxyethylene) chain and poly(oxypropylene) chain. A 3 and 4 digit code number indicates the molecular composition. When four digits are employed, the first two explain the average molecular weight of the hydrophobe (poly(oxypropylene) branches on the alkylenediamine). When three digits are used only the first number serves this purpose. The last digit of each code number represents the weight percentage of hydrophilic (poly(oxyethylene)) units to the nearest 10 percent. The tetrol compounds in the examples are described this way.  
  As diamines upon which the tetrols are based, in addition to ethylene diamine. diamines of a hydrocarbon containing 1 to 13 carbon atoms, preferably the lower alkyl diamines, where the lower alkyl radical contains 1-6 carbon atoms, can be used.  
  The polyepoxy compounds can be prepared by the method taught in British Pat. No. 793,915. Example 1. The other classes of compound can be similarly prepared. as in Example 10 in US. Pat. No. 3,008,884.  
  Typical of the acids and their esters to provide the chain-extending difunctional radical are the dialkyl phthalic, isophthalic or terephthalic esters. such as dimethyl terephthalate andadipic, phthalic, terephthalic sebacic, glutaric. pimelic, isocinchomeronic acids and their esters.  
  Typical of the polyepoxy compounds which provide the difunctional or divalent compounds, used to chain extend the tetrols based on diamines, are those polyepoxy compounds described in British specification No. 793,915 to Union Carbide on page 2, line 48 to line Also useful to form chain-extending divalent radicals are the aromatic or aliphatic diisocyanates. having a structure OCN-RNCO, where R is defined as above.  
  The antistatic fiber of this invention may also contain conventional fiber additives such as antioxidants, stabilizers. delusterants, dyeing assists, and colorants.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention will now be further described in the following specific examples which are to be regarded solely as illustrative and not as restricting the scope of the invention. Parts are by weight.  
 EXAMPLE 1 This example shows a method of preparing a preferred antistatic additive of the type disclosed in US. application Ser. No. 294,971, filed Oct. 1 1, 1972. The instant chain-extended polymer is prepared from a tet- 2 fTfz OCN-C H-C H2-HC H-NCO Ct 2 Elsi...  
 (molecular weight 262.4) was added dropwise to the material in the flask. Agitation was continued for 1 hour at ll05C. after the addition was completed. Then the product was cooled to room temperature. It was a soft solid having a melt viscosity of 8,300 centipoises at 100C. measured with the Brookfield viscometer. The viscosity of the original Tet&#39;ronic 1504 was 200 centipoises at 100C.  
 EXAMPLE 2 A glass reactor equipped with a heater and stirrer was charged with a mixture of 1,520 grams of ecaprolactam and 80 grams of aminocaproic acid. The mixture was then flushed with nitrogen and was stirred and heated to 255C. over a 1 hour period at atmospheric pressure to produce a polymerization reaction. The heating and stirring was continued at atmospheric. pressure under a nitrogen sweep for an additional 4 hours in order to complete the polymerization. During the last 30 minutes of the polymerization, 1.7 grams of 4,4&#39;-butylidene-bis-(6-tert. butyl m-cresol) and 48 grams of the antistatic compound of Example 1. were added to the polycaproamide and stirring was continued to thoroughly mix the additives throughout the polymer. Nitrogen was then admitted to the glass reactor and a small pressure was maintained while the polymer was extruded from the glass reactor in the form of a polymer ribbon. The polymer ribbon was subsequently cooled. pelletized. washed and then dried. The polymer was a white solid having a relative viscosity of about 55 to 60 as determined by a concentration of l 1 grams of polymer in 100 milliliters of 90 percent formic acid at C. (ASTMD-789-62T).  
  The polycaproamide pellets containing the antistatic agent and phenol additive were melted at about 285C. and then melt-extruded under a pressure of about 1500 psig through a 16-orifice spinnerette, each of the orifices having a diameter of 0.014 inch, to produce a 250-denier fiber. The fiber was then collected at about 1,000 feet per minute and was drawn about 3.5 times its extruded length to produce a 70-denier yarn. For convenience, this yarn hereinafter will be called Yarn A. A control yarn containing the antistatic agent but no additional additive was produced in the same manner as described above. For convenience, this yarn hereinafter will be called YarnB. A second control yarn containing no antistatic compound and no phenol comfabric test samples having a width of 3 inches and a length of 9 inches. The fabric samples were tested for their antistatic property in accordance with the general procedure described in the Technical Manual of the American Association of Textile Chemists and Colorists. 1969 edition. Volume 45. at pages 206-207. This test procedure is entitled Electrostatic Clinging of Fabrics: Fabric-to-Metal Test&#34; and is numbered AATCC 115-1969. In accordance with this test. Yarn C showed poor antistatic properties. i.e., the average time for fabric samples to decling from metal completely on their own was over 300 seconds after 5 to 25 wash cycles. in contrast. Yarn A and Yarn B both showed excellent antistatic properties. for example. average time for fabric samples to decling from metal completely on their own was about 120 seconds after 25 wash cycles. Yarn A. Yarn B and Yarn C were also tested for the number of nubs per pound as shown in Example 3.  
 EXAMPLE 3 This example outlines the method used for locating. identifying and calculating the nubs per pound in Yarn A. Yarn B and Yarn C as prepared in Example 2. In this methoda nub is defined as an enlarged place in a filament which is no more than several filament diameters in length. This method may be used for either monofilament or multifilament yarns; however. it is not applicable to most types of crimped yarn.  
  In accordance with the test. the -denier yarn is drawn directly from the package by means of an air aspirator and is passed through an opening of known width, specifically, 0.0030 inch in width. Such an opening is conveniently provided by use of a ceramic cleaner gap, which is well-known in the art. The presence of a nub is detected when it stops the yarn passage through the opening. The filaments are separated and the cause of the yarn stopping identified as a nub or as the twisted end of a broken filament. For representative results, about grams of yarn is passed through the gap and the number of nubs counted. Table 1 below shows the results of testing on Yarn A. Yarn B and Yarn C.  
 TABLE 1 Determination of Nubs Per Pound Yarn Sample Nub Count Per Pound o1- Yarn Yarn A 3.500 Yarn 13 17.850 Yarn C 2.300  
  lt will be noted that polyamide yarn made without additives had a relatively low nub count of 2.300 nubs per pound of yarn. Addition of the antistatic compound to the polyamide caused the nub count to increase to 17,850 per pound of yarn. However, the addition of the antistatic compound plus the phenol compound of the invention reduced the nub count to 3,500 nubs per pound of yarn.  
 EXAMPLE 4 The procedure of Example 2 (Yarn A) was followed except that the various additives were charged with the caprolactam initially. The antistatic fiber nub count was only 3,200 per pound of yarn.  
 EXAMPLE EXAMPLE 6 The procedure of Example 2 (Yarn A) was followed except that the antistatic additive was obtained from the reaction product of Tetronic 1504 and dimethyl terephthalate in a I to 0.7 mol ratio. The additive has a melt viscosity of 1.600 centipoises at 100C.  
  Sixty grams of the antistatic compound was added together with 1.13 grams of 4.4&#39;-butylidene bis-(6-tert. amyl m-cresol) and 6.4 grams of 50 percent aqueous TiO- dispersion. The fiber nub count was 3.160 per pound of yarn.  
 EXAMPLE 7 The procedure of Example 2 (Yarn A) was followed except that 90 grams of the antistatic additive of Example 6 was used together with 1 gram of 4.4&#39;-heptylidene bis-(6-tert. butyl m-cresol). The fiber produced had a low nub count of 3,245 nubs per pound of yarn.  
 EXAMPLE 8 Polymer pellets were prepared in accordance with Example 2 which contained 90 grams antistatic agent of Example 1 together with 2.7 grams of 4.4- butylidene bis-(o-tertbutyl-m-cresol). were melted at about 285C. and then melt extruded under pressure of 1.500 psig to a 70-orifice spinnerette, each of the orifices having a diameter of 0.0 l 8 inch to produce a fiber having about 4,500 denier. The fiber was collected at about 1.000 feet per minute and was drawn at about 4 times the extruded length to produce yarn having a denier of about 1 125. This yarn will hereinafter be called Yarn D. A control yarn containing no antistatic agent or phenol additive was prepared in the same manner as described above. This yarn will hereinafter be called Yarn E.  
  The yarns were textured using a steam jet and then two-plied by twisting two ends together with a 1 /2 S twist. The yarns were tufted into a level loop 20 02. carpet at about 6.5 stitch rate. about 9/32 to 10/32 inch pile height. dyed and latexed. Static buildup of the car-.  
 pet was tested by measuring the electrostatic voltage buildup on a person walking with a series of steps on a.  
 piece of carpet according to the standard CR1 Walk Test for static propensity in carpets. also labeled AATCC 134-1969. Carpet was conditioned at 70F. at percent relative humidity. Results are shown in the following Table.  
 Carpet Static Walk Test Made with Yarn D 4.9 KV Made with Yarn E 14.1 KV  
 The untextured yarn was also tested for nubs using the EXAMPLE 9 Ninety-four parts of polyhexamethylene adipamide and six parts of the antistatic material of structure of Example 1 and 0.18 parts of 4,4&#39;-butylidene-bis-(6-tert butyl-m-cresol) are melt blended by mixing the additive with the molten polyamide at about 285C. The melt is extruded from a spinneret and the fibers are drawn as described in Example 8. Carpet samples prepared from this fiber and tested in accordance with Example 8 showed a static build-up of 5.2 KV.  
 EXAMPLE l0 (Comparative) 1n comparative tests with antistatic yarns containing various commercially available hindered phenol compounds. the yarns of the present invention showed significantly greater breaking strength retention after exposure to light in conventional tests.  
  The antistatic additive used may be purchased commercially or prepared as follows: Three hundred grams of Tetronic 1504 (molecular weight 12,500) was placed in a three-neck flask fitted with a thermometer, stirrer. and addition funnel. The Tetronic 1504 was stirred and heated to 105C., and 4.2 grams of dimethyl terephthalate (molecular weight 194.2) was added to the material in the flask. Agitation was continued for about 3 hours at 200C. after the addition was completed. Then the product was cooled to room temperature. It was a soft solid having a melt viscosity of about 10,000 centipoises at 100C., measured with the Brookfield viscometer. The viscosity of the original Tetronic 1504 was 200 centipoises at 100C.  
  The yarns were tested in accordance with the following procedure: The yarns were wound onto 2.75X6.5 inch metal plates in single layers and exposed to Xenon-Arc Lamp for 200 hours; the test apparatus was operated in accordance with AATCC test method 16E- 197 l -Co1orfastness to Light: Water-Cooled Xenon-Arc Lamp. Continuous Light. Breaking strength of single filaments (in pounds) was determined before and after exposure to the light, using an lnstron Constant Rate of Elongation Tensile Tester and an average was obtained for 10 replications. The standard deviation (8) was about 0.5 pound. The percent breaking strength retained (percent B.S. Ret.) was calculated as follows:  
 Final Breakin Stren&#39;th Original Breaking Strength I00 /r B.S. Ret.  
 PART A (Use of 4,4&#39;-butylidene-bis-(6-tert. butyl m-cresol) A glass reactor equipped with a heater and stirrer was charged with a mixture of 1520 grams of e-caprolactam and grams of aminocaproic acid. The mixture was then flushed with nitrogen and was stirred and heated to 255C. over a 1 hour period at atmospheric pressure to produce a polymerization reaction. The heating and stirring was continued at atmospheric pressure under a nitrogen sweep for an additional 4 hours in order to complete the polymerization. During the last 30 minutes of the polymerization. 2.7 grams of 4.4-butylidene-bis-(6-tert. butyl m-cresol) and grams of the above-stated antistatic compound were added to the polycaproamide and stirring was continued to thoroughly mix the additives throughout the polymer. Nitrogen was then admitted to the glass reactor and a small pressure was maintained while the polymer was extruded from the glass reactor in the form of a polymer ribbon. The polymer ribbon was subsequently cooled. pelletized. washed. and then dried. The polymer was a white solid having a relative viscosity of about 55 to 60 as determined by a concentration of 1 1 grams of polymer in 100 milliliters of 90 percent formic extruded length. and plied to produce a 2.250-denier yarn having a denier of about 16 per filament. Hereinafter. this yarn will be called Yam 1. When Yarn I was exposed to light in accordance with AATCC test method 16E-l971. the percent breaking strength retained was 61 percent.  
  A control yarn containing the 4.4&#39;-butylidene-bis-(6- tert. butyl m-cresol) but no antistatic agent was produced in the same manner as described above. Hereinafter. this yarn will be called Yarn 11. When Yarn 11 was exposed to light in accordance with AATCC test method 16E-1971. the percent breaking strength retained was 82 percent.  
  The difference between Yarn l and Yarn 11 is significant at a level greater than 99 percent. This indicates that the amount of phenol compound utilized in the present process should be maintained as low as practically consistent with obtaining suitably reduced nub formation in the fiber.  
 PART B (Use of lrganox 1010) The procedure of Part A (Yarn l) was followed except that 2.7 grams of lrganox 1010 was added to the polymer instead of 2.7 grams of 4.4-butylidene-bis-(6- tert. butyl m-cresol). lrganox 1010 is sold commercially and has the structure:  
  C CH -O-C-CH -CH PART C (Use of 4,4&#39;-butylidene-bis-(6-tert. butyl m-cresol) The procedure of Part A (Yarn I) was followed except that 8.1 grams of the 4,4&#39;-butylidene-bis-(6-tert.  
 &#39;butyl m-cresol) was added to the polymer together with the 90 grams of the antistatic agent. Hereinafter, the resulting yarn will be called Yarn lV. When Yarn IV was exposed to light in accordance with AATCC test method 16E-1971. the percent breaking strength retained was 56 percent.  
  The difference between Yarn l and Yarn IV is significant at a level greater than 99 percent. Although the percent breaking strength retained in Yarn 1V is considered adequate. the lower value as compared with Yarn 1 shows the criticality of the amount of the sterically hindered phenol compound used.  
 PART D (Use of lrganox 1076) The procedure of Part C (Yarn IV) was followed except that 8.1 grams of lrganox 1076 was added to the polymer instead of 8.1 grams of 4.4&#39;-butylidene-bis-(6- tert. butyl m-cresol). lrganox 1076 is sold commercially and has the structure:  
 (CH C C (CH 3 -COOC H mg 2 1s 37 PART E (Use of lrganox 565) The procedure of Part C (Yarn IV) was followed except that 8.1 grams of lrganox 565 was added to the polymer instead of 8.1 grams of 4.4&#39;-butylidene-bis-(6- tert. butyl m-cresol). lrganox 565 is sold commercially and has the structure:  
 SC H  
 (CH 3 r 8 81.7 E1  
 3 3 SC Hl7 Hereinafter, the resulting yarn will be called Yarn V1. When Yarn V] was exposed to light in accordance with AATCC test method 16E-1971, the percent breaking strength retained was 32 percent.  
  The difference between Yarn IV and Yarn V1 is significant at a level greater than 99 percent. This shows the criticality of the specific sterically hindered phenol compound used.  
 PART F (Use of lrganox 1010) The procedure of Part C (Yarn IV) was followed except that 8.l grams of lrganox ll0 was added to the polymer instead of 8.1 grams of 4,4&#39;-butylidene-bis-(6- tert. butyl m-cresol). lrganox l0l0 is sold commercially and has the structure:  
 c CH2-O-C-CH2CH-2 0H C(CH Hereinafter, the resulting yarn will be called Yarn Vll. When Yarn VI] was exposed to light in accordance with AATCC test method l6E-l97l, the percent breaking strength retained was 21 percent.  
  The difference between Yarn IV and Yarn Vll is significant at a level greater than 99 percent. This shows the criticality of the specific sterically hindered phenol compound used.  
 PART G (No Phenol Compound Used) PART H (Dye Lightfastness) The dye lightfastness of yarns described above was determined for several acid shades and disperse shades on exposure to Xenon-Arc light (AATCC test method l6E-l97l The time required for a color break was similar as determined by the standard procedure regardless of the specific hindered phenol compound H(OCH H (oea used in the yarn; however, the intensity of the color break was less for yarn samples containing the 4,4&#39;-butylidene-bis-(6-tert. butyl m-cresol) of the present invention. In the case of Yarn Vlll, which contained no hindered phenol compound, time for color break was significantly less than the yarns containing the above-described hindered phenol compounds.  
 DISCUSSION In additional tests it was determined that the molecular weight of the tetrol compound used to prepare the chain-extended antistatic compound is preferably between about 4,000 and about 50,000, the ethylene oxide moieties making up about 10 to about percent of the molecular weight of said compound. Preferably, the antistatic fiber contains from about 2 to about 8 percent of the chain-extended antistatic compound. Normally, the chain-extended antistatic compound has a melt viscosity of 800 to 50,000 centipoises at l00C.  
  By antistatic&#34; fiber is meant fibers that will pass the cling test and shuffle test as described in US. Pat. No. 3,657,386. By fiber&#34; is meant multi-filament yarn, monofilament, and all the known physical forms of synthetic fibers. By polyamide is meant the polymers made by condensation of diamines with dibasic acids or by polymerization of lactams or amino acids, resulting in a synthetic resin characterized by the recurring group CONH. By ethylene oxide moiety&#34; is meant the portion of the chemical molecule -(CH C- H O).  
 We have found that the novel antistatic polyamide fiber of the present invention not only has relatively low nubs per pound of fiber, but in comparative tests with antistatic yarns contains various commercially available hindered phenol compounds, the present fiber showed unusual or unexpected results in that the present fiber showed significantly greater breaking strength retention after exposure to light in standard tests. Further, we have found that the quantity of the instant phenol compound contained in the present antistatic fiber is critical. That is. if the percentage of said phenol compound is too low, the occurrence of nubs in the fiber will not be sufficiently reduced; but if the percentage of said phenol compound is too high, the breaking strength retention of the fiber after exposure to light will be too low. Accordingly, the present invention is restricted to the production of antistatic fiber containing about 0.5 to 12 percent. preferably l to 6 percent, based on the weight of the antistatic compound, of the specific phenol compound of the inven-- 9 9% CI-I )y(OCHCH c ylH CHO) a (CH CH O) H CH \N-A-N CH r 3 CH Z (OCHCH (CH CHO) (CH CH O) H where a, b, c, w, .v, y and z are each a whole number and. A is a difunctional radical from a hydrocarbon containing 1 to 13 carbon atoms, said tetrol compound having a molecular weight between about 4,000 and about 50,000, and at least one compound selected from the group consisting of compounds which yield the following divalent radicals:  
 pound which is a chain-extended reaction product of a tetrol compound represented by the formula:  
 H (OCH2CH y (OCHCH (CH CHO) a (CH CH O) H (1H N-AN (1H H(OCH CH z (OCHC (CH CHO) (CH CH O) H where R is an alkyl hydrocarbon group containing less than nine carbon atoms and R is a tertiary alkyl group containing at least four but not more than 12 carbon atoms.  
  2. The process of claim 1 wherein the ethylene oxide moieties make up about to about 90 percent of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at lO0C.  
  3. The process of claim 2 wherein the phenol compound is selected from the group consisting of 4,4- butylidene bis-(6-tert. butyl mcresol); 4,4&#39;-butylidene bis-(6-tert, amyl m-cresol); and 4,4&#39;-heptylidene bis- (6-tert. butyl m-cresol).  
 F 4. The process of claim I wherein l to 6 percent based on the weight of the antistatic compound, of the phenol compound is dissolved in the extrudate.  
  5. The process of claim 4 wherein the ethylene oxide moieties make up about 10 to about 90 percent of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at 100C.  
  6. An antistatic polyamide fiber having less than 4 l0 nubs per pound of fiber, said fiber containing about I to 12 percent by weight of an antistatic comwhere a. b, c. d. w, .r, y and z are each a whole number and A is a difunctional radical from a hydrocarbon containing l to 13 carbon atoms, said tetrol compound having a molecular weight between about 4.000 and about 50,000, and at least one compound selected from the group consisting of compounds which yield the following divalent radicals:  
 where R&#39; is a difunctional radical from a hydrocarbon containing 1 to 30 carbon atoms; and about 0.5 to 12 percent by weight. based on the weight of the antistatic compound. of a phenol compound of the formula:  
 bU-O-m where R is an alkyl hydrocarbon group containing less than nine carbon atoms and R is a tertiary alkyl group containing at least four but not more than twelve carbon atoms.  
  7. The fiber of claim 6 wherein the ethylene oxide moieties make up about 10 to about percent of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at lO0C.  
  8. The fiber of claim 7 wherein the phenol compound is selected from the group consisting of 4,4&#39;-butylidene bis-(6-tert. butyl m-cresol); 4,4&#39;-butylidene bis-(6-tert. amyl m-cresol); and 4.4&#39;-heptylidene bis-(6tert. butyl m-cresol).  
  9. The fiber of claim 6 wherein the fiber contains 1 to 6 percent by weight. based on the weight of the antistatic compound, of the phenol compound.  
  10. The fiber of claim 9 wherein the ethylene oxide moieties make up about 10 to about 90 percent of the molecular weight of the tetrol compound and the chain-extended antistatic compound has a melt viscosity of about 800 to 50,000 centipoises at C.  
 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3 ,876,725  
 lN\/ ENTOR(S) Rodney vLee Wells and Lamberto Crescent ini It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 1, line 12, &#34;294,941&#34; should read 294,97l.  
 Column 4, line 35, &#34;3,008,884&#34; should read 3,009,884.  
 Column 12, line 30, &#34;contains&#34; should read --containing.  
 Signed and Sealed this 7 twenty-fourth D ay 0f February 1 9 76 [SEAL] A ttest:  
 RUTH. C. MIA-SON C. MARSHALL DANN 44116811118 0/11? (&#39;nmmissimwr njParems and Trademarks