US2196758A - Treating cellulose derivative materials - Google Patents

Description

Patented Apr. 9, 1940 UNITED STATES TREATING Joseph B. Dickey Rochester, N. Y.,

Company, Rochester,

1 New Jersey No Drawing.

CELLULOSE DERIVATIVE MATERIALS and James B. Normington, assignors to Eastman Kodak N. Y., a corporation of Application June 8, 1939,

Serial No. 278,140

16 Claims.

This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed of organic derivatives of cellulose such as cellulose acetate, cellulose propionate, cellulose acetate propionate, and cellulose acetate butyrate, to render them more amenable to textile operations such as knitting and the like. This invention also relates to compositions of matter in which cellulose derivatives such as cellulose acetate, cellulose nitrate or cellulose ethers are combined or mixed with other substances, such as a compatible plasticizer, and a common solvent for both, with or without other useful addition agents, so that the resulting product will have properties such as will make the composition highly advantageous for use in the plastic and analogous arts, such for instance, as the manufacture of wrapping sheets, photographic film, artificial silk, varnishes or lacquers, and the like.

As is well known in the manufacture of yarns, particularly those composed of or containing cellulose organic derivatives, it is necessary to treat the yarn in order to reduce the tendency toward breakage of the individual filaments or fibers when they are subjected to various mechanical strains and to lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, winding and reeling. It is also necessary to treat yarn to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In knitting, it is particularly important that the yarn be soft and pliable in order that it may conform readily to the contour of the needles and thus produce a closely knit fabric free from such defects as stitch distortion, pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such as polyhydric alcohols and similar agents as ingredients of yarn conditioning or lubricating formulas, generally in connection with mineral, animal or vegetable oils. It has been found, however, that most of the known softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is high vapor pressure, and in some cases too drastic a solvent action on the yarn. Many of such agents possess slight or insufficient solvent power for the lubricants with which they are used, and it is accordingly necessary to employ blending agents or emulsifying agents in order to obtain operable yarn treating formulas. In addition, many. of the known softening and lubricating agents are insufllciently soluble in water to permit satisfactory removal by aqueous scour baths.

While in the plastic and related arts cellulose acetates, nitrates and ethers have been known for decades, it has also been known that to utilize 6 them it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlomaphthalene or the like. Certain of these and other addition agents are also added for the purpose of reduc- 10 ethers to prepare them for use in the other plas- 20 tic arts, such as in the manufacture of lacquers, varnishes, artificial silk filaments, moulded compounds and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to 25 which cellulose derivatives have been put and the increasing number of desirable properties required of the cellulose derivative for most purposes has made the discovery of new and economical plasticizers or other addition agents a matter of considerable importance to the art.

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed of or containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns more amenable to knitting and other textile operations. A further and specific object is to pro-: vide a class of conditioning agents which augment or assist the lubricating action of various lubri cants when applied to such yarns. A still further object is to provide yarn softening and lubricating formulas which can be readily removed from the yarns by the usual scour baths. A still further object is to provide an improved method for the conditioning of yarns, particularly those composed of or containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object is to provide an improved type of yarn which is especially amenable to textile operations including circular knitting, weaving, spin- .which may be made into permanently transparcut, strong and flexible sheets or films of desired thinness which are substantially waterproof, are unaffected by ordinary photographic fluids and possess the desired properties of a support for sensitive photographic coatings. Yet another object of our invention is to produce a composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such as in the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, and to produce a composition which will not injure, or be injured by, the'substances or surfaces with which it is associated during manufacture. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene glycols may be used as yarn conditioning agents and particularly as softening agents, with or without the addition of animal, mineral, or vegetable oils, in the treatment of yarns composed of or containing organic derivatives of cellulose. We have found that these compounds when employed as described in the detailed examples set forth below have a slight solvent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at the same time having too drastic an action thereon.

These compounds are most conveniently prepared by reacting the desired alcohol with an anhydride or an acidwith or without catalysts or solvents as illustrated in the examples which follow. Our invention also comprises the discovery that valuable properties may be induced in and/or contributed to compositions containing cellulose derivatives such as cellulose acetate and other organic acid esters of cellulose, and to various synthetic polymers acetals, esters, ethers,halides and the like, polystyrene, polyindine and the various resins derived from acrylic acid and its derivatives by adding thereto .as plasticizing compounds the above-mentioned substances.

The following table includes a list of typical compounds which we have found to be useful for the purpose of our invention:

2-nitro-2-methylpropylene-l, 3-diacetate ..B. P. 30/1 mm. 2-n1tro-2-methylpropylene-l, 3-acctatepropionate B. P. l28-33/2 mm. 2-nitro-2-methylpropylene-1, 3-acctatchutyratc. B. P. lZ330/1 mm, 2-nitro-2-mcthyipropylcne-l, 3-propionatcbutyrate D. P. 12832/1 mm. Z-nitro-zmethylpropylcnc l, 3-dibutyrate B. P. l35-40/l mm.

2-nitro-2 methylpropylcnc-1, 3-dicaproatc B. P. l6l5/l mm. 2-nitro-2-methylpropylcnel, 3-di m c t h oxyace-B b to B. P. 12030/1 mm. 2-nitro-2-mcthyipropylcne-l, 3-dipropi0nate B. P. l24l27/1mm. 2-nitro'2-mcthylpropylened, 3-d isalicylatc M. P. 97l00. Z-uitro-Z-mcthylpropylenel, 3-d1anisate M. P. 104-5.

Examples of the preparation of typical compounds of this type are as follows:

including polyvinyl Pnm'mrron or .2-111110-2-mnmrnmz-13-nr- ANIBAIII -68 parts of 2-.nitro-2-methylpropanedlol-1,3- dianisate, 160 parts anisic acid, 500 parts toluene and 5 parts sulfuric acid are distilled in such a manner that the toluene is separated from the water of reaction and returned to the reaction vessel. When 18 parts of water have been collected, the mixture is cooled and the solid which separates is collected, washed and recrystallized from alcohol, M. P. 104-5".

Similarly there may be prepared: '-2-nitro-2- methylpropylene-1,3-disalicylate, M. P. 97-400". Also by the above procedure, using an equimolecular mixture of propionic and i-butyric acids, we obtain 2-nitro-2-methylpropylene-1,3-propionate \i-butyrate, B. P. 120-30/1 mm.

Psnrann'rron or 2-Nrm2-umni'maoPYwNE-L3-or- PBOPIONATE 68 parts 2-nitro-2-methylpropanedio1-1,3 and parts propionic anhydride are heated on a steam bath for three hrs. The propionic acid and excess propionic anhydride are distilled off and the ester is distilled under reduced pressure. There is obtained an excellent yield of 2-nitro-2- methylpropylene 1,3-dipropionate, boiling at 124-127/ 1 mm.

TREATMENT or Tmx'rmn Yuma In accordance with the invention these compounds may be applied directly to the yarn during or after spinning, or maybe added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and animal oils and accordingly they may be, and preferably are, employed as ingredients of yarn conditioning or lubricating formulas in conjunction with agents which function wholly or partially as lubricants.

' In the following examples-and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Example 1 Example 2 Parts Olive oil 50-99 1,3-dihydroxy-Z-nitropropanedibutyrate 50-1 This mixture is applied to textile materials such as silk, wool, viscose, cellulose acetate, etc. as described in Example 1. If the yarn is intended primarily for knitting, the amount of conditioning liquid applied may vary between 2-25% by weight of the yarn, and if for weaving the amount of liquid applied may vary between 1 and 5% by weight of the yarn. Cellulose acetate filaments or fibers treated as described above are quite soft and pliable and give improved results in various textile operations such as weaving. knitting, etc.

by weight of the yarn, if the yarn Example 3 Example 12 Parts Parts Olive oil 99-1 Mineral oil 30 3-nitropentanediol-2,4-oleate (mono) 1-99 Naphtheny1a1coho1 5 Blown neats-foot oil- 30 T1118 is applied to textile materials such as Silk, a wool, cotton, cellulose acetate and the like as 5 gighoxyethyladipate 2 described in Example 1. If the yarn is intended primarily for knitting, the amount Of OOIldltlOIl- 2 nnropropanedicflfuroate oleate ing liquid applied may vary between 2 and 25% by weight of the yarn, and if for weaving, the Example 13 Parts amount of liquid may vary between 1 and 5%. Oleic acid 2243 Cellulose acetate filaments or fibers treated as Blown i'a 25 described above are quite soft and pliable and B1 Ow n teaseed on 25 give improved results in various textile operations such as weaving, knitting, and the like.

Other examples of yarn conditioning compositions which may be applied to various types of yarns, particularly thos composed of or containing cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and similar cellulose organic acid esters in accordance with our invention and which render such yarns soft and pliable and especially well adapted for various textile operations, particularly knitting, are as follows:

Example 4 Parts 1,3 ditetrahydrofuryl-2-nitropropanediol- 1,3-dioleate -99 B-methoxyethylsuccinate 25-1 Example 5 Parts 1,3-diphenyl 2 nitropropanediol-1,3-oleatestearate 75-99 Tetrahydrofurfurylformal 25-1 Example 6 Parts 2-ethyl-2-nitropropanediol-1,3diacetate 1- 40 Olive oil 99-60 Example 7 Parts 2 propyl 2-nitropropanediol-1,3-dimethoxyacetate 60-70 Blown olive oil 39-25 Triethanolamine phosphate 1-5 Example 8 Parts Neats-foot oil '75 2 butyl 2-nitropropanediol-1,3-acetatebutyrate 20 Diethanolaminepropionatebutyrate 5 Example 9 Parts Blown neats-foot oil 53 Sodium sulfate 2 Oleic acid l0 Sulfonatecl castor oil 10 3 -lauiyl-3-nitropentanediol-2A-dilactate- 25 Example 10 Parts Mineral oil 99-50 2 nitropropanediol 1,3 acetatenaphthenate 1-50 Example 11 Parts Sperm oil 45 Butylnaphthenate 20 Tetrahydrofurfuryltetrahydrofuroate 20 tanediaceta 15 Sodium sulfate 2 Disodium salt of acetone phosphonate 1-10 2-methyl-2-nitropropanediol acetate propionate 25 Example 14 Parts Water Water-soluble cellulose ester 5 Glycerol acetone n 5 2-nitropropanediol-1,3-dilactate 10 Example 15 Parts Water 80 Water-soluble cellulose ether 5 2-nitro-2-methylpropanediol diacetate 10 Sulfonated olive oil 5 Example 16 A 20% solution of cellulose acetate propionate in acetone in which is incorporated 1-25% by weight of 2-nitro-2-methylpropanediol-distearate is extruded through fine orifices into an evaporative atmosphere. The filaments thus produced are wound, or twisted and Wound. Yarns thus produced are of dull luster and suitable for knitting.

Any of the above compositions may be applied to the yarn intended for use in circular knitting by means of a bath, wick, spray, roller, pad or any suitable means. The amount of conditioning liquid applied may vary between 5-25% by weight of the yarn. Usually, however, the amount of conditioning liquid applied is about 10-15% by weight of the yarn. Yarn composed of cellulose acetate conditioned as described above gives excellent results when used in the circular knitting process.

As will be apparent from the above examples and description the conditioning agents of our invention may be applied by a wide variety of methods. For example, we may employ the agent as an ingredient of the spinning dope from which the filaments are formed, the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent combination used in making up the spinning solution, and the degree of softness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith, or the liquid may be applied by immersion, spray, or otherwise. The particular point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the :odet or other roll or guide and the point of winding and/or twisting. In some cases, the iquid may even be applied to the yarn. after vinding onto cones, spools, bobbins, 'or the like rr by the so-called bobbin to bobbin method. '11 the case of staple fiber manufacture, the liq- Lid may be applied to the yarn prior to, or after :utting into staple lengths.

The amount of the agent so employed will 'ary widely depending upon the results desired, he specific nature of the material to which the agent is applied, the use to which the yarn is :ventually to be put and other factors. For ex- .mple, in a given'case where a cellulose organic .cid ester yarn such as a yarn composed of celluose acetate, is intended for knitting, about 4 o 25% or more by weight, based on the weight f the dry yarn, may be satisfactory, while if he yarn is intended for weaving, the amount may vary between about 1 and Although in the above examples we have reerred primarily to yarn treating compositions ontaining only the conditioning agent and an il, other ingredients ch as solvents, non-sclents, emulsifying agen s; blending agents and he like, may be added within the scope of our avention. Likewise, various dyes or other colorog matter may be included in case it is desired 0 permanently or fugitively tint or dye the maerial undergoing treatment.

Although we have found it convenient to illusrate our invention by reference to compositions ontaining specific percentages of the various inredients, these percentages may vary widely deending upon the particular purpose for which he composition is intended. For example, if it desired to control the solvent or softening aclon of the conditioning agent, the amount of he agent may be adjusted as, for example, by educing the amount of the agent andcorrepondingly increasing the amount of oil or other igredient.

While we have described our invention with articular reference to the treatment of yarns omposed of organic derivatives of cellulose such s cellulose acetate, the conditioning agents and )rmulas described herein are applicable to the onditioning of many other types of cellulose erivative yarns such as those composed of or mtaining cellulose propionate, cellulose butyrate, ellulose acetate propionate, cellulose acetate utyrate, ethyl cellulose, methyl cellulose, benzyl ellulose and others, as well as to the condition- 1g of silk, wool, cotton, viscose and other natral or artificial materials.

The term "yarn as used herein and in the aims is to be understood as including a single lament, a plurality of filaments associated into 1e form of a thread, either of high or low twist, ngle or multiple threads associated or twisted )gether, composite threads composed of a mixire of natural and artificial filaments or a comosite thread formed by twisting together indildual strands of' natural or artificial materials, well as cut staple fibers produced from natural ad/or artificial filaments or threads and spun irn produced from such staple fibers.

As indicated above, the yarn conditioning gents of our invention are exceptionally good ilvents for a wide variety of mineral, blown and oblown, drying and semi-drying animal and agetable oils such as cottonseed, olive, castor, cat's-foot, sperm and other oils. This enables 1cm to be used with any of such oils in making Butyl phthala up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and compositions of our intention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especiallythose composed of or containing organic derivatives of cellulose such as cellulose acetate and render them soft and pliable and amenable to various textile operations, especially operations such as those involved in weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in the manufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch distortion, laddering and the like.

Usn or COMPOUNDS AH Pms'rrcrznas Cellulose aceta 2-methyl-2-nitropropanediol-1,3-diacetate Acetone Example 18 Parts Cellulose acetate 100 2-nitropropanediol-1,3-dipropionate Metha 100 Acetone 300 Example 19 Parts Cellulose aceta 100 2 -ethyl 2-nitropropanediol- 1,3-acetatepropionate Ethylene chloride 300 jDinxanP 100 Example 20 Parts Cellulose aceta 100 3-ethyl-3-nitropentanediol-2,4 -ditetrahydrofuroa Triphenylphosphate Acetone Ethylaceta Example 21 Parts Cellulose acetate propionate 100 20 4-nitro-3,5-dihydroxyheptanedilaurate 30 Propylene chloride 100 Ethyl lactate 100 Acetone Example 22 Parts .Ce1lu1ose nitrate 100 Example 23 Parts Cellulose butyrate 100 1,3-ditetrahydrofuryl-1,3-

dihydroxypropanedivalerate 20 Propylene chloride 300 Acetone 100 Example 24 Parts Cellulose acetate butyrate 100 2-nitro2-methylpropanediol-1,3-dibutyrate- 30 Triphenylthiophosphate 10 Camphor 10 Ethylene chloride 400 Methanol 100 Example 25 Parts Cellulose ether 100 z-methyl-2-nitropropanediol-1,3-diacetate 60 Dioxane 300 Compositions of matter prepared as above described may be deposited upon any suitable film forming surface to form a film or sheet, as is well known to those skilled in the art. A film so produced has permanently brilliant transparency and low infiammability, burning no more readily than ordinary newsprint. Such film is exceedingly tough and flexible, as shown by the fact that it will withstand many folds upon a modified Schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for a considerable number of days to air maintained at a temperature of 65 C. the film still maintains flexibility (in contrast to almost complete lack of flexibility where no plasticizer is used) demonstrating that the film will withstand ordinary usage satisfactorily for many years. The sum total of the above-advantageous properties of a product produced from our new composition is considerably in excess of that of products produced with what have previously been regarded as the better plasticizers.

Other similar solvents than those mentioned above which are compatible with cellulose acetate and our new plasticizers may also occur to those skilled in this art. In like manner our plasticizers may be compounded with other single or mixed organic esters of cellulose, such as cellulose aceto-stearate, aceto-malate, or cellulose nitro-acetate, the cellulose ethers, and resins above mentioned, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer beingemployed.

Our novel plasticizers may be employed also with advantage in connection with a number of the known lacquer and varnish formulas with which it may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative or resin solution and, if non-solvents are added, only to such an extent as will not precipitate the derivative or resin from solution. Also the plasticizer is usually employed in larger amounts, such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of our invention will also suggest themselves to those skilled in the art and are to be included within the scope of the 5 claims appended hereto.

What we claim is:

1. The process of conditioning yarn to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane andalkene glycols.

2. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene glycols.

3. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of knitting, weaving, spinning and the like, which 4 comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of 4 mono-nitroalkane and alkene glycols, and a textile lubricant.

5. A conditioning agent for rendering yarns more amenable to textile operations including knitting, weaving, spinning, and the like which 5 comprises an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene glycols.

6. A conditioning agent for rendering textile yarns composed of or containing organic derivatives of cellulose more amenable to textile operations including knitting, weaving, spinning and the like which comprises an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene glycols, and a textile lubricant.

7. Textile yarns amenable to textile operations including knitting, weaving, spinning and the like impregnated with a lubricant containing as its 6, essential lubricating and softening component an ester selected from the group consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene glycols.

8. Textile yarns composed of or containing or- 7 ganic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning and the likejimpregnated with a conditionin agent comprising an ester selected from the group consisting of the aliphatic, aromatic and hetero- 7.

yclic acid esters of mono-nitroalkane and alkene lycols.

9. Textile yarns composed of or containing oranic derivatives of cellulose amenable to textile perations including knitting, weaving, spinning nd the like, impregnated with a conditioning gent comprising an ester selected from the roup consisting of the aliphatic, aromatic and eterocyclic acid esters of mono-nitroalkane and lkene glycols, and a textile lubricant.

10. A composition of matter comprising a cel- [1088 derivative and an ester selected from the roup consisting of the aliphatic, aromatic and eterocyclic acid esters of mono-nitroalkane and .kene glycols.

11. A composition of matter comprising cellose acetate and an ester selected from the rum: consisting of the aliphatic, aromatic and heterocyclic acid esters of mono-nitroalkane and alkene giycols.

12. A composition of matter comprising cellulose acetate and 2-nitro-2-methylpropy1ene- 1,3-dibutyrate.

13. A composition of matter comprising cellulose acetate and 2-nitro-2-methylpropylene- 1,3-dipropionate.

14. As a new chemical compound 2-nitro-2- methylpropylene-1,3-dibutyrate.

15. As a new chemical compound 2-nitro-2- methylpropylene-1,3-dipropionate.

16. As new chemical compounds testers selected from the group consisting of the aliphatic,

aromatic and heterocyclic acid esters of mono- 15 nitroalkane and alkene glycols.

JOSEPH B. DICKEY. JAMES B.'NORMINGTON.