US3274014A

US3274014A - Stabilized yarn compositions

Info

Publication number: US3274014A
Application number: US269156A
Authority: US
Inventors: Jr Robert C Harrington; James L Smith
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1963-03-29
Filing date: 1963-03-29
Publication date: 1966-09-20
Anticipated expiration: 1983-09-20
Also published as: DE1470803A1

Description

United States Patent 3,274,014 STABILIZED YARN COMPOSITIONS Robert C. Harrington, .Ir., and James L. Smith, Kingsport, Tenn., assignors to Eastman Kodak Company,

3,274,014 Patented Sept. 20, 1966 ing compounds according to our invention. ferred form of titanium dioxide is rutile.

The surprising nature of our invention is confirmed by the fact that the metal alky-l phosphates, phosphites The pre- Rochester, NY a corporation of New Jersey 5 and phosp-honates used, especiallythe zinc compounds, No Drawing. Filed Man 29 1963, sen Nm 269156 themselves show no appreciable light absorption either 9 Claims 1. 10 177 before or after exposure to sunlight and apparently when used as yarn ultraviolet stabilizers act by some other This application is a continuation-in-part of Harringmechanism than that of known yarn ultraviolet staton et a1. U.S. patent application Serial No. 147,749, filed 10 bilizers, many of which are thought to act as a reduc- October 26, 1961, and now abandoned. ing agent or absorbers for certain portions of the light This invention relates to man-made fibers and fabrics spectrum. Although we do not wish to be bound by made therefrom, and more particularly to such fibers and any particular theory as to why the yarn additives of fabrics resistant toultraviolet light. our invention are effective :as ultraviolet stabilizers for Man-made fibers and fabrics are susceptible to degman-made fibers and fabrics, it may be that the metal radation by ultraviolet light. For example, synthetic part of the compounds exerts the sunlight-inhibiting efpolymer yarn, as exemplified by cellulose ester yarn, fect. loses both stretch and strength on exposure to light. Our invention will be further illustrated by the follow- Hence, filaments made from cellulose esters, modacrylics, ing examples. In these examples, yarns were spun in polyesters, poly-a-olefins, halogenated synthetic resins the conventional manner, the cellulose acetate being spun and the like would not be used in some end products, such from acetone solutions of a secondary cellulose acetate as window curtains or drapery linings. It therefore apcontaining about 28% acetyl, the modacrylic from a dipears desirable to render such yarn resistant to ultramethyl formamide solution, and the halogenated polyviolet light. mer from an acetone solution. The cellulose ester yarns, one Object of our invention is to Provide nad all 150 denier with 38 filaments, were separately woven fibers and fabrics which are resistant to ultraviolet light. as filling into a 75 denier bright acetate warp. The fabric Another object of our invention is to provide man-made wa a 5 harness satin 180 ends and 70 picks per inch. filaments which are resistant to ultraviolet light. Other The rough or back side of the fabrics tested was about objects of our invention Will appearherein. 80% filling. This side, which was predominately the We have found that yarn compositions having incoryarn being tested, was exposed to light for different porated therein a small amount of a metal monoalkyl or periods of time. After exposure, strips of the fabric were monoafyl Phosphate, metal dialkyl P p metal raveled to one inch wide strips and cut, in the direction alkyl Phosphonate, mfillal alkyl y' P P Or of the filling, into 8 inch long strips. These strips were metal dialkyl phosphite are resistant to ultraviolet light. ulled apart i t th filling with a In tm Tensile We have found Zinc, Chromium and aluminum salts to Tester. The elongations of the strips and the pounds give best ultraviolet stabilization and of these zinc to necessary to break the fabrics were recorded and the be preferred. Preferred metal salts we have found usepercent less in strength and elongation was calculated. ful in stabilizing man-made fibers and fabrics against The test is referred to in the examples as the ravel strip deterioration from ultraviolet light are zinc ethyl phoste t, phate, zinc diethyl phosphate, zinc dimethyl phosphate, 40 EXAMPLE 1 i ethyl (ethyl phosphorlaitwizinc propyl phosphite Cellulose acetate yarns containing 1.4% titanium Zmc ethyl PhOSPhPHate Zmc dlpropyl Phosphate Zmc dioxide and other cellulose acetate yarns containing 1.4% lauryl phosphate, zinc stearyl phosphate, zinc butyl p titanium dioxide and 1% of various zinc salts were tested phate, chromium diethyl phosphate and aluminum ethyl by the ravel strip test after fabrics woven therefrom had P P The ethyl derivatives are to be Preferred been exposed under glass to sunlight for different periods especially Zinc ethyl P P of time. The samples were inclined at a 45 degree angle We have found that a small amount of titanium dioxide to the ho i o facing outh, The results are listed in may be used in conjunction with the phosphorus-contain- Table I.

Table I Langley Units of Light Yarn Tested 30, 000 70, 000 120, 000

Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss in Strength in Elongation in Strength in Elongation in Strength in Elongation Control, no stabilizer 12. 6 23. 4 75.0 92. 8 84. 3 94. 0 Zinc monoethyl phosphate, stabilizer- 0. 5 11. 3 l6. 7 13. 2 24. 0 35. 0 Zine isopropyl phosphate 2. 0 12. 8 l8. 5 15. 7 33. 5 46. 3 Zine diethyl phosphate- 1. 3 10. 4 17. 7 17.8 32. 7 44. 2 Zinc ethyl phosphonate. 6. 0 13. 0 l9. 5 20. 7 41. 3 55. O Zinc dipropyl phosphite. 4. 6 11. 2 l5. 3 l5. 7 40. 1 39. 7 Zine ethyl (ethyl phosphonate) 5.1 10. 7 21. 2 30. 1 50. 3 58. 5

10,000 Langley units of light are equivalent to exposure to Florida summer sunlight for one E onth under glass.

3 4 It may be seen from the above table that the incorpora- Table IV tion of a small amount of the salts of the invention in yarn, containing a dulling pigment, reduces the loss of Langley Units (1,000)

Percent strength and elongation caused by exposure to sunhght. sample Zinc Ethyl Percent 40 so 40 80 Phosphate TiOz Percent Loss in Percent Loss in EXAMPLE 2 Elongation Pounds Cellulose acetate filaments containing no dulling 'pig- Contr1o11 18 .3g S e 1... ment and cellulose acetate filaments containing 1% of amp various zinc salts of the invention were tested in the weathepomem manner described in Example 1. The examples are shown Control 2... 0 0 s7 75 m Table II Sample 2... 1 0 0 78 61 Table II Langley Units of Light Yarn Tested 30, 000 70, 000 120, 000

Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss Percent Loss in Strength in Elongation in Strength in Elongation in Strength in Elongation Control, no stabilizer 7. 3 25. 6 40. 2 84.0 78. 3 90.0 Zinc monoethyl phosphate... 0.0 14. 7 14. 3 12. 7 19.8 30. 5 Zinc diethyl phosphate 0.2 11.7 15.0 14.5 30.7 40.8 Zine ethyl phosphonate 3. o 10. 5 17. 6 19. 9 40. 2 50v 7 Zinc ethyl (ethyl phosphonate) 4. 3 10. 5 20. 7 29. 7 50. 1 57.0

The above Table II shows the reduction of the loss of EXAMPLE 5 strength and elongation of fabrics which contain a small amount of zinc alkyl phosphates and the like.

EXAMPLE 3 Various concentrations of zinc monoethyl phosphate were incorporated in dull cellulose acetate yarn containing 1.4% TiO to determine the efiFect of various concentrations of stabilizer 0n the rate of degradation of the filaments. The samples were exposed and tested as in Example 1, and the results are lited in the following table.

Table III 40,000 Langley Units of Light Percent Zinc Monoethyl Phosphate in Yarn Percent Loss in Percent Loss in Strength Elongation Control, no stabilizer 15. 7 31. 2 92% 13. 5 20. 1 .5%.. 12.3 19.4 1.0%. 9.1 10. 3 2.0%.... 9.1 9.2

EXAMPLE 4 Zinc monoethyl phosphate and rutile titanium dioxide were incorporated in Verel modacrylic yarn by adding to the dope from which the filaments were spun and the yarn evaluated for ability to resist degradation by ex- .posure to Langley units of light and in a Weather-Ometer. The results are given in the following table.

EXAMPLE 6 An amount of zinc (ethyl phosphonate) equal to 1% based on polymer weight was added to a 27% acetone dope of a modified vinylidene ohloride-acrylonitrile copolymer (about 50:50). Yarn spun from this dope was tested in a Fade-Ometer and showed no discoloration after hours exposure to ultraviolet light. A control containing no additive and tested under the same conditions turned brown in 20 hours.

EXAMPLE 7 An amount of zinc bis[ethyl('ethyl phosphonate)] equal to 1% based on the polymer weight was incorporated into a 27% solids in acetone dope of a modied vinylidene chloride-acrylonitrile copolymer (about 50:50). Fibers spun from this dope were tested in a Fade-Ometer and showed no discoloration after 80 hours exposure to ultraviolet light. A control containing no additive and tested under the same conditions turned brown in 20 hours.

EXAMPLE 8 An number of phosphate compounds were tested for their ability to stabilize yarn against photodegradation by sunlight. Cellulose acetate was the fabric used in this instance. The results of these tests are reported in the following table.

Table V Fabric Properties Weather-Ometer Exposure 2 Original Sample No. Additive 1 600 Hrs. 1,200 Hrs.

Strength, Percent Toughness Strength, Percent Toughness Strength, Percent Toughness lbs. E 3 (S XPerlbs. E 3 Retained, lbs. E 3 Retained,

cent E Percent Percent 78526 1.0% Chromium Diethyl 22.7 23. 522.1 17.0 13.0 42. 3 17. 3 68 22.

Phosphate. 78527 1.0% Ziuc Lauryl Phos- 25. 0 30.0 750.0 19. 5 18. 2 47. 3 16. 7 50 11.1

phate. 78528 1.0% Zinc Diethyl Phos- 23. 3 28. 3 659. 4 21.3 22. 0 71. 1 20. 3 19. 2 59. 0

p ate. 78529 1.0% Aluminum Ethyl 23. 4 27. 3 638. 8 19.1 18. 2 54. 4 15.1 6.0 14. 2

Phosphate. 78530 1.071.; Zinc Phenyl Phos- 25. 7 29. 7 763. 3 18.9 16.0 39. 6 16. 8 10.0 22.0

p ate. 78531 1.0%; Zine Stearyl Phos- 22. 5 23. 3 524. 2 15.9 5. 3 16. 1 11. 0 3.3 6. 9

p ate. 78532 1.0? Zinc Butyl Phos- 22. 4 31.0 694.4 '21. 8 21. 3 66. 9 17.2 10. 3 25. 5

p late. 78612 Control 26. 5 37. 3 988. 4 13. 3 4. 3 5. 8 13. 7 4. 0 5. 5

1 Added to cellulose acetate yarn containing 1.4% T103. 2 Weather-Ometer equipped with sunshine carbon are. 3 Elongation.

4 Strength.

Zinc dialkyl phosphate (2) Zinc alkyl phosphates and zinc alkyl and aryl (alkyl and aryl phosphonates) wherein the alkyl or aryl groups may be methyl, ethyl, isopropyl, n-propyl, butyl,

lauryl or stearyl.

O O 0 Zn li R Zn O-l -O-R O I t 2 Zinc alkyl Zinc alkyl (alkyl phosphonate phosphonate) (3) Zinc dialkyl phosphites where the alkyl groups include methyl, ethyl, isopropyl, n-propyl, 'butyl, lauryl or stearyl. Preferably, the alkyl group of the zinc salts is ethyl, zinc monoet-hyl phosphate being particularly useful.

When metals other than zinc are used according to our invention the above formulas may be simply changed to substitute the Cr or Al or the like for the Zn and modify the structure to reflect the difference in valence.

For economic reasons, We prefer to employ about .5 to 2% of the Zinc salts of the invention, based on the weight of the cellulose ester. A somewhat wider range, say 0.1 to 5%, may generally be incorporated with good results. Concentrations greater than 5% are detrimental to the properties, such as toughness, of the cellulose ester.

Representative of the cellulose esters which may be stabilized according to our invention against deterioration caused by lengthy exposure to sunlight, especially ultraviolet rays, are the lower fatty acid esters of cellulose,

e.g., cellulose acetate and triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate; inorganic acid esters of cellulose such as cellulose nitrate; and, cellulose ethers such as ethyl cellulose.

We have found that it is advantageous in some instances to incorporate a dulling pigment in cellulosic compositions stabilized against the effects of ultraviolet light in accordance with our invention. This dulling pigment as indicated above may for example be any form of titanium dioxide, rutile titanium dioxide being especially useful.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A man-made filament yarn composed essentially of a fiber-forming composition selected from the group consisting of cellulose esters, acrylonitrile copolymers, polyesters and poly-alpha-olefins stabilized against deterioration from ultraviolet light containing 0.1 to 5%, based on the weight of the yarn, of a salt selected from the group consisting of (1) metal salts of monoalkyl, monoaryl and dialkyl acid phosphates; 2) metal alkyl phosphonates and metal alkyl (alkyl phosphonates), and (3) metal dialkyl phosphites, said alkyl and aryl groups containing from 1 to 18 carbon atoms and said metal being selected from the group consisting of zinc, chromium and aluminum.

2. In the method of preparing cellulose acetate yarns wherein cellulose acetate is dissolved in a solvent and filaments are extruded therefrom, the step which comprises adding to the solution of cellulose acetate and solvent 0.5 to 2%, based on the weight of the cellulose acetate, of a compound selected from the group consisting of a metal monoalkyl phosphate, a metal monoaryl phosphate, a metal dialkyl phosphate, a metal alkyl phosphonate, a metal alkyl (alkyl phosphonate) and a metal dialkyl phosphite, said alkyl and aryl groups containing 1-18 carbon atoms, said metal being selected from the group consisting of zinc, chromium and aluminum, and a delustering amount of titanium dioxide.

3. Cellulose ester compositions containing .1 to 5%, base on the weight of the cellulose ester, of a compound selected from the group consiting of (1) metal salts of monoalkyl, monoa ryl and dialkyl acid phosphates, (2)

metal alkyl phosphonates and metal alkyl (alkyl phosphonates), and (3) metal dialkyl phosphites, said alkyl and aryl groups containing from 1 to 18 carbon atoms and said metal being selected from the group consisting of zinc, chromium and aluminum.

4. Cellulose ester compositions containing .1 to 5%;

based on the weight of the cellulose ester, of zinc monoethyl phosphate and a delustering amount of titanium dioxide.

5. Cellulose acetate compositions containing .1 to 5%, based on the weight of the cellulose acetate, of zinc monoethyl phosphate.

6. A man-made filament fabric of a yarn composed essentially of .a fiber-forming composition selected from the group consisting of cellulose esters, acrylonitrile copolymers, polyesters and poly-alpha-olefins stabilized against deterioration from ultraviolet light containing 0.1-5%, based on the weight of the yarn in said fabric, of a salt selected from the group consisting of (1) metal salts of monoalkyl, monoaryl and dialkyl acid phosphates, (2) metal alkyl phosphonates and metal alkyl (alkyl phosphonates), and (3) metal dialkyl phosphites, said alkyl and aryl groups containing from 1-18 carbon atoms and said metal being selected from the group consisting of zinc, chromium and aluminum.

7. A man-made filament fabric as defined by claim 6 wherein the fiber forming composition is" a cellulosic ester.

" "S.' A man-made filament fabric as defined by claim 6 wherein said salt is zinc monoethyl phosphate.

9. A man-made filament fabric as defined by claim 6 wherein the fiber forming composition contains from 0.1 to 5%, based on the Weight of the fabric, of rutile titanium dioxide.

References Cited by the Examiner ALEXANDER H. BRODMERKEL, Primary Examiner.

L. B. HAYES, Assistant Examiner.

Claims

1. A MAN-MADE FILAMENT YARN COMPOSED ESSENTIALLY OF A FIBER-FORMING COMPOSITION SELECTED FROM THE GROUP CONSISTING OF CELLULOSE ESTERS, ACRYLONITRILE COPOLYMERS, POLYESTERS AND POLY-ALPHA-OLEFINS STABILIZED AGAINST DETERIORATION FROM ULTRAVIOLET LIGHT CONTAINING 0.1 TO 5%, BASED ON THE WEIGHT OF YARN, OF A SALT SELECTED FROM THE GROUP CONSISTING OF (1) METAL SALTS OF MONOALKYL, MONOARYL AND DIALKYL ACID PHOSPHATES; (2) METAL ALKYL PHOSPHONATES AND METAL ALKYL (ALKYL PHOSPHONATES), AND (3) METAL DIALKYL PHOSPHITES, SAID ALKYL AND ARYL GROUPS CONTAINING FROM 1 TO 8 CARBON ATOMS AND SAID METAL BEING SELECTED FROM THE GROUP CONSISTING OF ZINC, CHROMIUM AND ALUMIMUM.