US3634236A

US3634236A - Spandex lubricant composition

Info

Publication number: US3634236A
Application number: US714429A
Authority: US
Inventors: James R Buster; Charles H Apperson
Original assignee: Union Carbide Corp
Current assignee: Viskase Corp
Priority date: 1968-03-20
Filing date: 1968-03-20
Publication date: 1972-01-11
Anticipated expiration: 1989-01-11

Abstract

A LUBRICATING FINISH FOR SPANDEX FIBERS AND THE LIKE COMPRISING A SOLUTION OF LIQUID SIOLOXANE AND A SURFACTANT IN MINERAL OIL.

Description

United States Patent Office 3,634,236 SPANDEX LUBRICANT COMPOSITION James R. Buster, St. Albans, and Charles H. Apperson,

Charleston, W. Va., assignors to Union Carbide Corporation No Drawing. Filed Mar. 20, 1968, Ser. No. 714,429 Int. Cl. D06m 13/18, 15/68 US. Cl. 252-8.9 26 Claims ABSTRACT OF THE DISCLOSURE A lubricating finish for spandex fibers and the like comprising a solution of liquid siloxane and a surfactant in mineral oil.

This invention relates to an improved lubricant finish for spandex type synthetic yarns. The requirements for an ideal lubricant finish for spandex are generally similar to those of other synthetic yarns in that a low uniform level of fiber to metal, fiber to ceramic and fiber to fiber friction should be provided without producing harmful effects to the yarn. Because of the tackiness of spandex yarns, a finish is required to prevent blocking, i.e., sticking of yarns to one another, and yet to provide easy removal of yarn for processing. It is desirable for the lubricant to be easily and uniformly applied to the yarns and yet be easily removed, preferably by aqueous scour prior to dyeing or other finishing operations. Most of the now available lubricants for spandex are undesirable as they either discolor the yarn, degrade fiber properties, are unstable solutions, require emulsification for applying, cannot be easily removed for further processing. Also some lubricants require that high (10-15 percent) percentages of the lubricant be added to the fiber to give adequate processability and this large amount of lubricant increases the amount of material which may come out of the fiber and give objectionable deposits on yarn processing equipment. Although lubricants of mineral oil and silicones have been used, they are either unstable and separate into original components, discolor or are viscous and exhibit poor wetting characteristics.

Examples of available lubricants for spandex fibers are talcum powder, textile oil compositions based on mineral oil and fatty acid esters, certain waxes which can be applied from melt and combinations of waxes and oils. All of these lubricants have deficiencies insofar as the noted requirements for an ideal finish for spandex is concerned. Talcum powder is messy and hard to apply. Mineral oil when applied in large amounts allows spandex yarn to stick to itself and cause blocking. Fatty acid esters have detrimental effects on yarn properties. Waxes are hard to apply and gum up processing equipment. Some mixed lubricants, e.g., mineral oil, waxes and silicones are unstable or must be applied from emulsion requiring the removal of water after application.

We have now discovered how to combine the good lubricating properties of mineral oil and the non-blocking properties of liquid siloxanes without the discoloration, lack of uniformity, poor wetting and high proportions of finish heretofore associated with such finishes. We achieve the fiber finishes of our invention by using mineral oil as a base to which is added a liquid siloxane soluble in the mineral oil and a surfactant or wetting agent which is also soluble in the mineral oil.

Mineral oil suitable for the invention includes any commercially available mineral oil having good lubricating properties and a viscosity between about and about 100 centistokes. A white mineral oil of about 50 centistokes viscosity is preferred.

The liquid siloxane must be one which is soluble in mineral oil. Particular liquid siloxanes useful in this in- 3,634,236 Patented Jan. 11, 1972 vention include those soluble in mineral oil which contain at least one siloxane group having the formula:

r R SiO Ha +1) 2 (1) wherein R is a monovalent hydrocarbon group having at least five carbon atoms or an alkoxy(polyalkyleneoxy) alkyl group, R is a monovalent hydrocarbon group, a hydroxyl group, an alkoxy group or a halogen-substituted monovalent hydrocarbon group, a has a value from 1 to 3 inclusive, b has a value from 0 to 2 inclusive, and (a+b) has a value from 1 to 3 inclusive.

The siloxanes useful in this invention can contain only groups represented by Formula 1 or they can contain both such groups and groups having the formula 2 (2) wherein R" is hydrogen, a monovalent hydrocarbon group having from 1 to 4 carbon atoms or an alkoxy group and c has a value from 1 to 3 inclusive.

One class of siloxanes useful in this invention are those soluble in mineral oil which are represented by the formula:

i R Si0(R SiO) (RSiO) SiR wherein Z is phenyl, beta-phenylethyl or octadecyl, R and R" are as defined above, d is an integer from 0 to 500, e is an integer from 1 to and ezd is preferably at least 0.2: 1.

When R in Formula 1 is an alkoxy(po1yalkyleueoxy)- alkyl group, then the siloxane is a siloxane-oxyalkylene block copolymer.

Among the siloxane-oxyalkylene block copolymers that are especially suited for use in this invention are those soluble in mineral oil and having the formula:

wherein Me" is a methyl group, m has a value from 0 to 25 inclusive, n has a value from 1 to 10 inclusive, x has a value from 0 to 25 inclusive, y has a value from 0 to 25 inclusive, z has a value from 2 to 3 inclusive and R" is hydrogen or an alkyl group containing from 1 to 4 carbon atoms inclusive.

Particular liquid siloxanes useful in the invention include the following:

A liquid siloxane of the formula CHzCHzCulL (CHs)aSiO[(CH SiO]2s[(CEa)SiO]nSi(CH having a viscosity at 25 C. of from 200 to 600 centistokes.

A liquid siloxane having the formula s n rslx wherein x is a whole integer of at least 2, and having a viscosity at 25 C. of from 1,000 to 30,000 centistokes. In order for the silicone of the latter formula to be an oil, it is recognized that some of the valences of oxygen must be chemically combined in cyclic structures and/ or linked to monovalent groups (e.g., ethyl or hydrogen).

A liquid siloxane of the formula CH SiOKCHs)2SiO]1(CH SiO) Si(CH3) CHzCHzCH (OC3Ho)120CH2CHzCH CHa A liquid siloxane of the formula (T121331 CH3SlOKCH3)2Si0]x(OH3SiO) Sl.(CH3)3 wherein x and y are each about 40 and the material is a semi-solid.

The surfactant used in our invention must be a good wetting agent and must be soluble in mineral oil. Our preferred surfactant is an ethoxylated aliphatic alcohol of the formula wherein R is an alkyl radical of from 8 through 20 carbon atoms and n has an average value from 3 through 8. In a more preferred alcohol of the above formula R is a linear alkyl radical of from 11 through 15 carbon atoms and n is to 7. Particular surfactants which are preferred include: C H (CH CH O) H, C H (CH CH O)-;H,

In the finish of our invention mineral oil constitutes at least 65 percent by weight of the finish. The liquid siloxane can be from 2 to as much as about 30 percent by weight and the surfactant from /2 up to about 5 percent. A preferred composition range is 97 to 77 percent by weight mineral oil, 5 to percent mineral oil soluble liquid siloxane and l to 3 percent mineral oil soluble surfactant.

EXAMPLES I-VII Spandex yarn of 140 nominal denier was spun by a wet spinning process from a dimethylformamide solution which contained percent by weight of a caprolactone polyester-based polyurethane-urea spandex polymer, pigmented with titanium dioxide and containing conventional stabilizer additives for protection from the degradative effects of ultraviolet light and oxidation. Without any lubricant added this yarn would not run through fiber handling machinery, could not be knitted and blocked badly. Lubricated with a conventional lubricant consisting of 84 percent by weight Marcol 52 white mineral oil, 11 percent by weight oleic acid and 5 percent by weight mixed isopropanol amines, the yarn had satisfactory friction characteristics but blocked badly and could not be knitted. Marcol 52 is made by the Humble Oil and Refining Co. of Baltimore, Md., and is a National Formulary grade of white mineral oil with a viscosity in Saybolt seconds of 51 at 100 F. and 33.7 at 210 F. It is free of aromatics and contains about 50 percent by weight paraffins and 50 percent mixed naphthenes of up to 5 rings.

When lubricated with a lubricant of the invention in Examples I through VII, however, the yarn did not block and had good knitting properties. The lubricated yarn had good friction properties as measured by the force in grams required to pull yarn over other yarn or over steel (column D of Table I). This is a dynamic measurement on running yarn measured on a Manra strainometer. The lubricant of the invention does not degrade the color of the yarn as was demonstrated by measuring the original whiteness of the lubricated yarn as the reflectance of light at 550 millimicrons (column B in Table I) and by measuring the fade index or rate of color change on a Fade- Ometer (column F).

In the table column A gives the weight percent of lubricant added (or add-on) as measured by hexane extraction of the lubricated yarn. In column B are given the relative proportions of mineral oil, liquid siloxane and surfactant respectively present in the lubricant. Column C gives the actual measured denier for each yarn. In the line C1 of Table I are shown the results for the yarn used in Examples I through VII when run using only water and no lubricant or finish and in line C2 are shown the results when lubricated with the conventional lubricant described above. The rest of Table I shows the results of the Examples I through XIII wherein the yarn was lubricated with the lubricant of the invention consisting of various proportions of white mineral oil (Marcol 52), liquid siloxane and a surfactant. The liquid siloxane was of the formula and had a viscosity at 25 C. of from 200 to 600 centistrokes. The surfactant in Examples I through V was the reaction product of a secondary linear aliphatic alcohol of about 15 carbon atoms ethoxylaed with about 6 moles 10 of ethylene oxide. In Example VI the surfactant was the reaction product of a secondary linear aliphatic alcohol of about 15 carbon atoms ethoxylated with about 5 moles of ethylene oxide while the surfactant in Example VII was the reaction product of a secondary linear aliphatic 15 alcohol of about 15 carbon atoms ethoxylated with about 3 moles of ethylene oxide.

TABLE I A B 0 D E t 20 Lubri- Iereent cant Friction lubripro- Orig Fad 0 Ex. cant portions Denier Yarn Steel white index 01 0 125 85.7 .55 C2 4.5 138 3.0 10.2 80.8 .50 4. 5 89/10/1 131 3.8 12.5 85. 8 .50 It 5. 7 88 10/2 135 4. 0 13. 5 87.1 .53 5. 4 85/10/15 135 4. 0 11. 2 s5. 2 .51 4.1 04/5 1 133 4.1 12. 0 85. 5 .50 8. 0 79/20/1 138 3. 4 12.0 85. 7 .55 4. 8 89/10/1 134 3. 8 12. 5 86. 3 .50 5. 3 89/10/1 131 3. 8 12. 5 87.2 .54 4.1 04/5 1 128 4. 2 13. 0 87.1 .55 4. 2 89/10/1 133 3. 0 12.0 85. 0 .55 3.1 94/5/1 130 3. 9 11.8 86. s .52 4. 0 88/10/2 135 4. 0 13. 3 85. 8 .55 4. 0 94/5/1 132 3. 7 12.0 85. 0 .53

EXAMPLES VIII AND IX The procedures and materials were identical with those in Examples I through V except that a different batch of spandex polymer was used which gave slightly different values in the control samples C3, C4 and C5 in Table II. Control sample C3 contained no lubricant and was run with water only with the results listed. Control C4 was lubricated with mineral oil only and the results are as listed for the sample. This sample blocked badly and could not be knitted normally. Sample CS was lubricated with a conventional lubricant consisting of 84 percent by weight Marcol 52 white mineral oil, 11 percent by weight oleic acid and 5 percent by weight isopropanol amines. This sample also blocked badly and could not be knitted normally. Results are given in Table II.

TABLE II A B C D E F Lubri- Pereent cant, Friction lubripro- Orig. Fade Ex. cant portions Denier Yarn white 1ii(1(X C3 0 85.1 .55 C4 12.5 .5 4.) 83.2 .51. C5 11.7 .1 6.2 83.0 .30 VIII.. 9. 5 89/10/1 130 3. 25 8. 3 82. 6 42 IX.--. 12.0 79/20/1 134 4.1 8.5 81.2 .42 XIV. 8.5 70/20/1 132 3.8 9.2 80.6 .47 XVL. 11.0 89/10/1 130 3. 75 8.1 83. 0 .50 XVII... 15. 3 79/20/1 134 3.0 0.0 81. 5 .46

EXAMPLES X AND XI The procedures and materials were identical with those in Examples I through V except that the liquid siloxane was different, being of the formula EXAMPLES Xll AND Xlli The procedures and materials were identical wilh those in Examples I through V except that the liquid siloxane was different, being of the formula CH3Si0[(OHa)2SiO]7(OHaSiO)sSi(CHa)3 CHzH2CHz(OC3Hu)12O CH2CH2CH2CH3 EXAMPLE XIV The procedures and materials were identical with those in Examples XII and XIII except that a different batch of spandex polymer was used which gave slightly different values in the control samples C3, C4 and C5 in Table II, which samples were made as described for Examples VIII and IX. Results are given in Table II.

EXAMPLE XV The procedures and materials were identical with those in Examples I through V except that the liquid siloxane was different, being of the formula wherein x and y are each about 40 and the material is a semi-solid. Results are given in Table I.

EXAMPLES XVI AND XVII The procedures and materials were identical with those in Example XV except that a different batch of spandex polymer was used which gave slightly different values in the control samples C3, C4 and C5, which samples were made as described for Examples VIII and IX. Results are given in Table II.

EXAMPLE XVIII In this example the wetting times of two typical finish formulations of this invention were measured and compared to other formulations. Wetting time was determined by noting the time required for lubricant to pass through a particular quantity of fiber. Using this test, mineral oil alone required 64.8 seconds to wet through the sample while the addition of one part by weight of a liquid siloxane of the formula having a viscosity of 25 C. between 200 and 600 centistokes to nine parts by weight of mineral oil gave a solution which required 109.8 seconds to wet through. When the mineral oil and liquid siloxane were mixed with the reaction product of a secondary linear aliphatic alcohol of about carbon atoms ethoxylated with about 6 moles of ethylene oxide in weight proportion of 89 parts mineral oil, 10 parts liquid siloxane and 1 part surfactant, however, the resulting solution had a wetting time of only 88.2 seconds. By comparison, a commercially available two phase liquid mixture of mineral oil, silicone and butyl stearate required 359.1 seconds to wet through while another conventional lubricant consisting of 84 percent by weight Marcol 52 white mineral oil, 11 percent by weight oleic acid and 5 percent by weight isopropanol amines required 158.5 seconds.

EXAMPLE XIX In this example the wetting times of two typical finish formulations of the invention were measured and compared to other formulations. Wetting time was determined by noting the time required for lubricant to pass through a particular quantity of fiber. Using this test, mineral oil alone required 54.1 seconds to wet through the sample while the addition of one part by weight of a liquid siloxane of the formula to nine parts by weight of mineral oil gave a solution which required 83.8 seconds to wet through. When the mineral oil and liquid siloxane were mixed with the reaction product of a secondary linear aliphatic alcohol of about 15 carbon atoms ethoxylated with about 6 moles of ethylene oxide in weight proportion of 89 parts mineral oil, 10 parts liquid siloxane and 1 part surfactant, however, the resulting solution had a wetting time of only 55.5 seconds. By comparison, a commercially available two-phase liquid mixture of mineral oil, silicone and butyl stearate required 359.1 seconds to wet through while another conventional lubricant consisting of 84 percent by weight Marcol 52 white mineral oil, 11 percent by weight oleic acid and 5 percent by weight isopropanol amines required 158.5 seconds.

What is claimed is:

1. A lubricating finish for spandex fibers and the like consisting essentially of from 65 to 97 /2 percent by weight mineral oil, from 30 to 2 percent mineral oil soluble liquid siloxanes having at least one siloxane group of the formula:

wherein R is a monovalent hydrocarbon group having at least five carbon atoms or an alkoxy (polyalkyleneoxy) alkyl group wherein each alkyleneoxy group is ehtyleneoxy or propyleneoxy, R is a monovalent hydrocarbon group, a hydroxyl group or a halogen-substituted monovalent hydrocarbon group, a has a value from 1 to 3 inclusive, [1 has a value 0 to 2 inclusive and (a-l-b) has a value from 1 to 3 inclusive, and from 5 to /2 percent of a mineral oil soluble surfactant which is an ethoxylated alkyl alcohol.

2. A lubricating finish according to claim 1 wherein the proportion of mineral oil is from 72 to 94 percent by weight, the proportion of mineral oil soluble liquid siloxane is from 3 to 25 percent and the proportion of mineral oilsoluble surfactant is from 1 to 3 percent.

3. A lubricating finish according to claim 1 wherein said surfactant is an ethoxylated alkyl alcohol of the formula 'RO(*CH CH O) H wherein R is an alkyl radical of from 8 through 20 carbon atoms and n has an average value from 3 through 8.

4. A lubricating finish according to claim 1 wherein said surfactant is an ethoxylated alkyl alcohol of the formula RO(CH CH O),,H wherein R is an alkyl radical of from 11 to 15 carbon atoms and n has an average value of 5 through 7.

5. A lubricating finish according to claim 1 wherein said surfactant has the formula C H O(CH CH O) H.

6. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of the siloxane groups described in claim 1 and siloxane groups of the formula:

wherein R" is hydrogen, a monovalent hydrocarbon group having from 1 to -4 carbon atoms or an alkoxy group and c has a value from 1 to 3 inclusive.

7. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of compounds of the formula:

wherein Z is phenyl, beta-phenylethyl or octadecyl, R is a monovalent hydrocarbon group, a hydroxyl group or a halogen-substituted monovalent hydrocarbon group, R" is hydrogen, a monovalent hydrocarbon group having from 1 to 4 carbon atoms or an alkoxy group, d is an integer from 0 to 500, and e is an integer from 1 to 100.

8. A lubricating finish according to claim 7 wherein the ratio of e to d is at least 0.2 to 1.

9. A lubricating finish according to claim 1 wherein said liquid siloxane is a siloxane-oxyalkylene block co- 7 polymer consisting essentially of compounds of the formula:

wherein Me is a methyl group, m has a value from to 25 inclusive, n has a value from 1 to inclusive, x has a value from 0 to inclusive, y has a value from 0 to 25 inclusive, z has a value from 2 to 3 inclusive, and R" is hydrogen or an alkyl group containnig from 1 to 4 carbon atoms inclusive.

10. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of compounds of the formula:

having a viscosity at 25 C. of from 200 to 600 centistokes. 11. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of compounds of the formula:

[C H Sio wherein x is a whole integer of at least 2, and having a viscosity at 25 C. of from 1,000 to 30,000 centistokes.

12. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of compounds of the formula:

13. A lubricating finish according to claim 1 wherein said liquid siloxane consists essentially of compounds of the formula:

wherein x and y are each about 40.

14. Spandex fiber coated with at least 1 percent by weight of a lubricating finish consisting essentially of from 65 to 97 /2 percent by weight mineral oil soluble liquid siloxanes having at least one siloxane group of the formula:

wherein R is a monovalent hydrocarbon group having at least five carbon atoms or an alkoxy (polyalkyleneoxy) alkyl group wherein each alkyleneoxy group is ethyleneoxy or propyleneoxy, R is a monovalent hydrocarbon group, a hydroxyl group or a halogen-substituted monovalent hydrocarbon group, a has a value from 1 to 3 inclusive, [2 has a value 0 to 2 inclusive, and (a-l-b) has a value from 1 to 3 inclusive, and from 5 to /2 percent of a mineral oil soluble surfactant which is an ethoxylated alkyl alcohol.

15. Spandex fiber according to claim 14 wherein the proportion of mineral oil in the lubricating finish is from 72 to 94 percent by weight, the proportion of mineral oil soluble liquid siloxane is from 3 to 25 percent and the proportion of mineral oil soluble surfactant is from 1 to 3 percent.

16. Spandex fiber according to claim 14 wherein said surfactant is an ethoxylated alkyl alcohol of the formula RO (CH CH O) H wherein R is an alkyl radical of from 8 through 20 carbon atoms and n has an average value from 3 through 8.

17. Spandex fiber according to claim 14 wherein said surfactant is an ethoxylated alkyl alcohol of the formula RO(CH CH O),,H wherein R is an alkyl radical of from 11 through 15 carbon atoms and n has an average value of 5 through 7.

[8. Spandex fiber accordirg to claim 14 wherein said surfactant has the formula C H O(CH CH O) H.

19. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of the siloxane groups described in claim 14 and siloxane groups of the formula:

wherein R" is hydrogen, a monovalent hydrocarbon group having from 1 to 4 carbon atoms or an alkoxy group and c has a value from 1 to 3 inclusive.

20. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of compounds of the formula:

2 Ry'siO(R2"sio) (R'sio),siR,"

wherein Z is phenyl, beta-phenylethyl or octadecyl, R is a monovalent hydrocarbon group, a hydroxyl group or a halogen-substituted monovalent hydrocarbon group, R is hydrogen, a monovalent hydrocarbon group having from 1 to 4 carbon atoms or an alkoxy group, d is an integer from 0 to 500 and e is an integer from 1 to 100.

21. Spandex fiber according to claim 14 wherein the ratio of e to d is at least 0.2 to 1.

22. Spandex fiber according to claim 14 wherein said liquid siloxane is a siloxane-oxyalkylene block copolymer consisting essentially of compounds of the formula:

wherein Me is a methyl group, In has a value from 0 to 25 inclusive, :1 has a value from 1 to 10 inclusive, x has a value from 0 to 25 inclusive, y has a value from 0 to 25 inclusive, 2 has a value from 2 to 3 inclusive and R" is hydrogen or an alkyl group containing from 1 to 4 carbon atoms inclusive.

23. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of compounds of the formula:

CHzCHzCaHs 3)3Sl 3)2slO]2u[( 3)SlO]n H3)3 having a viscosity at 25 C. of from 200 to 600 centistokes.

24. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of compounds of the formula:

wherein x is a whole integer of at least 2, and having a viscosity at 25 C. of from 1,000 to 30,000 centistokes.

25. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of compounds of the formula:

26. Spandex fiber according to claim 14 wherein said liquid siloxane consists essentially of compounds of the formula:

cu sioltolimsromomsro),snout);

wherein x and y are each about 40.

References Cited UNITED STATES PATENTS 3,445,385 5/1969 Vartanian 2528.8 1,970,578 8/1934 Schoeller et a1 252-8.9 X 2,690,426 9/1954 Jefferson et al 2528.9 X 3,140,198 7/1964 Dawson et al. 3,277,000 10/ 1966 Chandler. 3,288,622 11/1966 Weiss 1l7139.5X 3,423,314 1/1969 Campbell ll7139.5 X

HERBERT B. GUYNN, Primary Examiner Po-who UNITED STATES PATENT ()FFECE (W) "CERTIFICE oF cosncrlon Patent No. 3 $34,236 Dated January 11, 1222 Inventofls) James R, Buster and Charles H. Apperson It is certified that error appears in the above-identified patent and that said- Letters Patent are hereby corrected as shown below:

Column 2 line 3 R should read R Column 2, line 17, R "SiO should read R" SiO Column 2 line 28 R "SiO(R "SiO) (R'Si0) SiR should a read -::R'f3SiO (Rf' SiO)a(R'Si0) SiR" Column 3 line 14, c n mn cu m a should read c sn mn cu m n Column 3 line 26 after "surfactant" and before 'Examples I-VII" a paragraph was omitted and should read:

--In the practice of our invention spandex fiber is coated with at least 17. by weight of the lubricating finish of the invention, with the total applied from 1 to 157. by weight.--

Column 3 line 61, Ometer should read ometer Column 4 line 9 7' ethoxylaed should read ethoxylated Column 5, line 69, cn sio [(011 9 5101 (cn sio) si(cn should read CH Si0[ (CH SiO] (CH3SiO') Si(CI-I Column 6, line 25, ehtyleneoxy should read ethyleneoxy Column 7 line 10 containnig should read containing LColumn a, line 17 R should read R" J Signed and sealed this 22nd day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER',JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents