CA1135918A - Process for surface treating cellulose products - Google Patents
Process for surface treating cellulose productsInfo
- Publication number
- CA1135918A CA1135918A CA000314744A CA314744A CA1135918A CA 1135918 A CA1135918 A CA 1135918A CA 000314744 A CA000314744 A CA 000314744A CA 314744 A CA314744 A CA 314744A CA 1135918 A CA1135918 A CA 1135918A
- Authority
- CA
- Canada
- Prior art keywords
- filaments
- liquid
- nonsolvent
- cellulose
- nonsolvent liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
PROCESS FOR SURFACE TREATING CELLULOSE PRODUCTS
Abstract of the Disclosure This invention relates to a process for treating the surface of cellulosic shaped products such as fibers, films, filaments, yarns and the like, formed from a spinning dope of a solution of cellulose in amine oxide, by applying to the surface of the product a nonsolvent liquid that will reduce the solvent action of the amine oxide for cellulose at the surface of the product.
Abstract of the Disclosure This invention relates to a process for treating the surface of cellulosic shaped products such as fibers, films, filaments, yarns and the like, formed from a spinning dope of a solution of cellulose in amine oxide, by applying to the surface of the product a nonsolvent liquid that will reduce the solvent action of the amine oxide for cellulose at the surface of the product.
Description
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In the process of forming filaments from an extrusion of a cellulose spinning dope, there arises the problem of surface tacking and/or fusion of fila-ments as they are brought in contact with each other at a point of collection. Such tacking and/or fusion of the Eilaments contributes to further difficulties in the continuing processing of -the filaments for their formation into yarn. Of interest in the prior art is the U. S. patent to Blades 3,767,756 which discloses a process for the spinning of filaments from a polyamide spinning dope and passing the filaments through a layer of inert noncoagulating fluid and into a coagulating bath before the filaments are brought together for further processing. Also, the patent to ~organ 3,414,645 is directed to a process for spinning wholly aromatic polyamide fibers in which the filaments after extrusion are passed through gaseous medium for a short distance to evaporate a small amount of the solvent before the fibers enter a coagulation bath, after which they are washed and stretched. None of the art, however, provides for a surface treatment of filaments formed from a solution of cellulose in amine oxide with a surface coating of a nonsolvent liquid that inhibits the fusing and/or tacking of the filaments together when they are collected.
This invention contemplates such a new process ;~
and provides for surface treating filaments extruded from spinning dope of a solution of cellulose dissolved in amine oxide, by applying to the surface of the :, ~
~L~3~ii~1Ei extruded filament, immediately after extrusion, a solu-tion of a nonsolvent liquid capable of rendering the amine oxide inactive as to its abi:Lity to form solutions with cellulose and thus reduce the tendency of tacking and/or fusion of filaments so that when they are collected together, surface tacking or fusing of adjacent filamen-ts is substan-tially reduced.
The coating of the filaments with the nonsolvent may be accomplished by passing them immediately after extrusion and before they are collected together into ~.
contact wi-th a surface that contains a continuous supply of a liquid which is nonsolvent for cellulose so that the surface of the filaments is continually coated with the nonsolvent liquid.
In addition to sur~ace coating of the filaments with the nonsolvent liquid, the surface of the filaments can be passed through a chamber having nonsolvent vapor laden atmosphere, such as a fog of minute particles or droplets of nonsolvent liquid, so that particles of the nonsolvent liquid are deposited on the surface of the filaments. In order to increase the deposition of the liquid particles on the surface of the extruded fila-ments an electrostatic charge can be placed on the filaments such that the surface of the filaments has a polarity opposite to that of the particles in the vapor laden atmosphere thereby increasing the attraction of the particles to the surface of the filaments.
Another method by which the extruded filaments may be coated with the nonsolvent liquid is by passing the filaments as extruded through a vapor layer of non-solvent liquid for a very short period of time and then ~3~L8 into a tank which contains the nonsolvent liquid, and then bringing the coated filaments together.
Still another method for coating the filam0nts with nonsolvent liquid is by extrusion of the filaments through a spinneret in which a plurality of jet openings, communicating with a chamber providing a continuous supply of nonsolvent liquid, are positioned adjacent to the spinneret orifices. By passing a nonsolvent liquid -through the jet openings in the spinneret as the fila-ments are extruded through the spinneret orifices, the surface of each filamen-t is immediately, or after a very short interval of contact with air in a gap between the spinneret orifices and the nonsolvent liquid, coated with nonsolvent liquid, thus preventing tacking or fusing of ~-filaments when they are brought together.
The extruded filaments of this invention can be ~-subjected to a drawing operation during the application of the nonsolvent with a major portion of the drawing of the filaments to induce improved physical properties therein being accomplished before the nonsolvent liquid coated filaments are collected together. Extruded filaments treated in accordance with the process of this invention, after being coated with the nonsolvent liquid, can be handled by conventional wet spinning equipment~
These and other objects will become apparent from the following description of the preferred embodiments `~-and examples and the accompanying drawings which illus-trate diagrammatically an apparatus which may be used to practice the process of this invention, in which drawings:
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FIGURE 1 is a schematlc view of an apparatus for carrying out the process of the invention, in which a nonsolvent liquid is applied to the filaments by a roller applicator;
F~GURE 2 is a schematic view of a modification of the roller applicator in FIGURE 1 showing spaced concentric grooves with filaments contacting the surface of the grooves in the surface of the roller applicator;
F~GURE 3 is a schematic view of a modification of FTGURE 1 in which the nonsolvent liquid is applied to the fila-ments by contact with the edge of a plate surface supportinga film of nonsolvent liquid;
FIGURE 4 is a schematic view of a modification of FIGURE 3 in which the plate has an annular~shaped contact sur-face containing a film of a nonsolvent liquid;
FIGURE 5 is a schematic view of a further embodiment o~ the invention showing an apparatus for applying nonsolvent liquid to the surface of the filaments passing through a cham-ber COntainLng aerosolized or atomized nonsolvent particles;
F~GURE 6 is a schematic view of still another embodi-~2Q ment of the invention showing an apparatus for applying non-solvent liquid to the surface of filaments as the filarnents pass through a vertical tube with nonsolvent liquid flowing ,:
through it; and F~GURE 7 is a schematic view of still a further embodi- 1 .
ment of the invention showing nonsolvent liquid flowing through jet openings in a spinneret plate adjacent to spinneret ori-fices and is located on the same sheet as FIGURE 1;
FIGURE 8 is a schematic view of stiIl another .
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embodiment of the invention showing an appartus for applying nonsolvent liquid to -the surface of filaments passing through a chamber containlng foamed nonsolvent liquid and is located on the same sheet as Figure 2.
In FIGURE 1 is illustrated the applying of a nonsolvent liquid to the surface of a spun filament formed from cellulose dissolved in amine oxide in accordance with this invention. The solution of cellulose in amine oxide can be made in a conventional manner, e.g. t by dissolving cellulose in an amine oxide solution in a heated tank, preferably under pressure or by any other means. For example, as illus-trated, solid cellulose sheets impregnated with the amine oxide solvent are added to a hopper and fed by an extruder 11 through a die port 12 to a metering b device 13 whereby the cellulose becomes completely dissolved in the amine oxide at the elevated temperature `~
and pressure in the extruder, then extruded or spun through a spinneret 14.
The use of an extruder to dissolve amine oxide-impregnated cellulose is more fully described in U.S. Patent No. 4,144,080.
The cellulose solution is continuously extruded from the spinneret 14 to form a plurality of filaments 15 which, due to the amount of tertiary amine oxide solvent present in their composition, must be carefully spaced from each other so that sticking or fusion of the filaments does !`
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not occur. To accomplish this, the spinneret orifices are patterned so that the extruded filaments remain spaced from one another until they are collected together for further processing. The filaments 15 pass downward through a small air space 16 in which some of the volatile solvent from the surface of the filaments is removed. All filaments are ext:ruded so that in their downward travel they contact a portion of the surface of an applicator roll 17 which can be driven at any speed in either direction, but preferably rotates in the same direction and at a peripheral speed less than the linear speed of the filaments to reduce the tendency of the filaments to fuse together. The rotating applicator roll 17 is positioned with its bottom portion imm2rsed in a trough 18 containing the nonsolvent liquid so that its surface maintains a constant supply of nonsolvent liquid for the coating in the filaments passing against its surface. Nonsolvent liquid is supplied to trough 18 from a supply tank 19 by a pump 20 to maintain a constant supply of nonsolvent liquid in trough 18. It will be appreciated that the surface of the applicator roll must be formed from a material that is capable of the proper degree of liquid pick-up so that its surface continuously presents an amount of liquid that will effectively coat the surface of the filaments when they are brought into contact with the surface o the applicator roll.
AEter the coating of the filaments with the nonsolvent liquid, they are brought together and passed around a turn:Lng godet roll 21 and then between feed rolls 22 to take-up roll 23. The filaments before ~, ~
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- ~35~
collection ancl passing over the godet 21 have their surface coated with a thin film of a nonsolvent which substantially eliminates tacking and/or fusing of adjacent filaments.
Advantageously, the surface of -the roller applicator 17 may have concentric spaced surface grooves 24 positioned so that individual filaments 15 can be guided during their contact with applicator roll 17.
It will be appreciated that the individual grooves 24 not only assist in maintaining filaments at a desired spaced interval from each other but also provide in the grooves a pool of nonsolvent liquid which assists in the efficiency of application of the nonsolvent liquid to the surface of the filaments, requiring less contact time in which the surface of the filaments must be in contact with the surface of the applicator roll 17 (see FIGURE 2).
It will be appreciated that in the roller appli-cation of the nonsolvent, the filaments can be directed so that the surface of the spaced filaments just kiss the surface of the roller applicator or can be brought into contact so that they maintain a contact with the roller surface over a segment of the surface. The amount of contact, of course, will depend on the ability of the surface of the applicator roll to pick up nonsolvent liquid and impart it to the surface of the filaments. It is important that the applicator roll have a pick-up surface that will not abrade or break the thread line while possessing the ability to pick up sufficient liquid and deposit it effectively on the surface of the filament during the period of contact.
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The roller applicator may be rotated in either direction, but when the roller applicator 17 is rotated in the same direction as the ~ilament travels, as illus-trated in FIGURE 2, at the point of tangency where the filament fi~st contacts the surface, the peripheral speed of the roller preferably should be less than the linear speed of the filament. In either case, the peripheral speed of the roller should be not less ~han a speed that will carry a sufficient amount o~ nonsolvent liquid to coat the filaments.
~ t will also be appreciated that the nonsolvent liquid can be applied to the roller applicator surface as by other means than by immersion of the applicator such as by spray nozzles or a doctor blade in which the liquid can be sprayed or doctored onto the surface of the roller to provide the desired amount of liquid to be applied to the surface of the filaments.
Another method of contact application of the nonsolvent liquid to the surface of the filaments is shown in FIGURE 3 in which the filaments 15 are brought into contact with a curved edge 28 or a plate 26 which has a downwardly tilted surface that terminates in the curved edge 28. Positioned in the surface of the plate applicator is a series of spaced outlets 30 through which continuously flows nonsolvent liquid that passes over the surface of th~ plates and then passes over the cur~ed edge so that the filaments 15 continuously contact the edge 28 where they are coated with the nonsolvent liquid.
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The outlets 30 are operatively connected to a supply line 31 through which the nonsolvent liquid is continuously supplied to the outlets by a pump 32 from a supply source 33 located under the applicator plate 26.
The nonsolvent liquid passing over edge 28 is collected in supply source 33 where it is recycled to the plate 26.
Another method of application of a nonsolvent liquid to the surface of the extruded filaments is shown in FIGURE 4 in which a donut-shaped applicator sur~ace 40 is used to apply the nonsolvent liquid to the extruded filaments. The filaments 15 are passed in contact with inner annular surface 41. ~he top of the donut-shaped applicator 40 has a series of spaced holes 43 which are operatively connected to a supply line 44 having a metering pump 45 which supplies a con-stant flow of nonsolvent liquid to the top surface of the donut-shaped applicator from a supply source 45, which is positioned under a godet roll 47 which is the point of collection of the filaments that have been coated with the liquid. The collected filaments from godet roll 47 are turned and passed through feed rolls 48, 48A and then to a take-up roll 49. The liquid after flowing over the inner annular surface 41 is coltected at the supply source. The position of the holes 43 is .. .
on the downward side of the top of the curved surface that forms the inner annular surface so that the liquid will flow towards and over this surface to supply the required amount of nonsolvent liquid to the filaments.
The direction of the liquid could be reversed so the . - ~
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liquid travels to -the outside edge of the donut, and the filaments are maintained in con-tact with the outside, rounded edge of the donut. Similarly, a flat horizontal circular plate with rounded edges can be used for applying nonsolvent li~uid to -the surEace of the filaments. It will be appreciated that in all plate applicator con-structions, the extruded filaments contact the edge of the plate and the spinneret orifices are patterned so that the filaments will be extruded so that their thread line will not make contact with each other until after the nonsolvent liquid has been applied.
It also will be appreciated that the spinning solution must have sufficient viscosity so that fila-ments formed from it will be able to withstand any forces that may be present during the period of contact with the applicator surface so that there is no breaking of the thread line. One skilled in spinning will be able to adjust the condition, i.e., spinning velocity~ the position of the applicator and the take-up speed, concentration of amine oxide in the spin bath to obtain a fiber of the desired denier and physical properties.
FIGURE 5 is another embodiment of the process ;
of the invention. In this embodiment a hopper 10 supplies solid cellulose and amine oxide solvent or 25 cellulose impregnated with amine oxide solvent to an extruder 11 which mixes the materials and where a solution is formed as previously mentioned and conveyed to a metering device 13. The metering device 13, which may be a pump, conveys a metered amount of the solution 30 through spinneret 14 to form continuously extruded . - ~ - ~ -. . . ..
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filaments 15. The ~ilaments 15 pass from the spinneret into the top of a fog chamber 51 containing an atmosphere laden with particles of nonsolvent liquid. The filaments pass through the fog chamber 51 into a lower chamber 52 where they are collected on a take-up roll 53 or further processed, e.g., cut into staple, washed, etc.
During their passage through the fog chamber, the particles of nonsolvent liquid are condensed onto the surface of the filaments to inactivate the solvent so as to cause precipitation of the cellulose on the surEace of the filaments, thus eliminating the tackiness at the surface and tendency of filaments to stick to each other. Nonsolvent liquid is collected in the lower "~ ~
chamber 52 and is recirculated by a pump means 54 through a liquid line 55 into the chamber 51 through an atomizing nozzle 56 positioned in the chamber 51.
Positioned in the lower chamber 52 is an outlet opening 57 for removal of air laden with nonsolvent liquid which is passed through a condenser means 59 with the air free of nonsolvent liquid exiting through opening 60 to the atmosphere and the condensed nonsolvent liquid passing through line 61 to pump means 54 where it ~-is recycled to atomizing nozzle 56.
~dvantageously, the fog chamber 51 may have more than one atomizing nozzle 56 spaced so that the fog chamber is provided with a substantially uniform atmos-phere laden with nonsolvent liquid particles to aid in ;-covering of the surface of the filaments with nonsolvent -liquid as the filaments travel from the spinneret to their -point of collection on the take-up roll.
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It will be appreciated -that the aerosolized or atomized nonsolvent particles must be rather small and must be introduced into the fog producing chamber in a manner so that there is a minimum of turhulance to prevent the filaments passing downwardly through the atomized particles from beiny swayed from their normal path.
Also, the concentration of suspended nonsolvent particles in the atmosphere must be sufficient so that the surface of all the filaments passing through the chamber 51 have atomized particles of nonsolvent deposited during substantially all of their travel through the cha~ber 51.
Advantageously, the extruded filaments may be electrically ¦
charged so t}iat the surface of the filament will attract suspended particles of li~uid. Suitable control means 62 can be provided to assure that the pressure in line 55 is maintained so that the proper quantity of nonsolvent liquid is passed through the nozzles to produce the desired atmosphere.
FIGURE 6 of the drawings shows a still further embodiment of the process of this invention. In this embodiment the filaments 15 are extruded from spinneret 14 through a small air space 16 and into an immersion tank 70 containing nonsolvent liquid. Exiting from the bottom -of immersion tank 70 is a downwardly extended tube 91 which exits into a lower tank 92. Connected to the bottom portion of tank 92 is a liquid supply line 75 which by pump means 74 transfers nonsolvent Iiquid ~rom lower tank 92 to immersion tank 70. The pump means 74 maintains a constant flow of nonsolvent from the lower tank 92 to immersion tank 70 to maintain the level in . . . i . . . , - ~ . ~ , . . .
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the immersion tank constant, thus xeplacing nonsolvent liquid that flows downward through vertical tube 91.
The filaments pass through the nonsolvent liquid in the ~mmersion tank and the extended tube 91 and pass over take-up rolls 95 where they are cut into staple fibers which are collected and removed for further fiber processing.
In air space 16 is maintained a constant vapor layer which may consist of an inert gas or a nonsolvent vapor or fog between the spinneret and the surface of the liquid in the immersion tank 70. It has been found that excellent results are o~tained when the gaseous or vapor layer through which the filaments pass is from about 0.5 cm to greater than 10 cm in length, F~GURE 7 of the drawings illustrates another embodi-ment of the invention in which the nonsolvent liquid is sprayed directly into the downward path of extruded filaments as they are formed. In this process the nonsolvent liquid is sprayed from ~ plurality of openings 90 in the face of the spinneret 14 pos~tioned adjacent to spinneret orifices. The filaments covered with nonsolvent liquid travel downwardly to a godet roll 71 where the filaments are collected and turned and pass ¦
through a pair of feed rolls 72, 72A to a take-up roll 73. ¦
The open~ngs 90 in the spinneret communicate with a supply of nonsolvent liquid which is ~orced through the opening ~y pump 74 hrough a supply line 75 2rom a supply ¦
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of nonsolvent liquid in a container 76. The sprayed non-solvent liquid which does not adhere -to the surface of the filaments falls by gravity into t.he container 76. The pump 74 maintains sufficient pressure in the liquid line 75 to assure that the proper quantity of nonsolvent liquid is spray-ed throuyh the opening 90 to provide jets of liquid that will effectively cover the surface of the extruded filaments before they arebrouyht together.
F~URE 8 is similar to FIGU~E 7 and the same numerals are used Eor like features. In FIGURE 8, the filaments are extruded or spun through the spinneret 1~ into a chamber 80 having an inlet 81 and an outlet 82 for the introduction of the nonsolvent and a foamy carrier, such as a surfactant, which can be foamed easily in mixing vessel 83 by mixing with the nonsolvent liquid and can easily be separated from the nonsolvent liquid. l'he foamy carrier provides for rapid and complete contact of the'~ilament as it leaves the spinneret by the'nonsolvent liquid. The preferred foamy carrier sur~
factant may be a nonionic surfactant such as ethoxylated fatty alcohols, ethoxylated fatty acids or ethoxylated(s) alkyl phenols or long-chain amine oxides, e.g., dimethyl coco amine , oxide, N-coco morpholine oxide.
During the application of the nonsolvent, the fila- ' ments can be drawn with a draw ratio of from 1:1 to about -1:100 with a major portion of the filament drawin~ being performed close to the spinneret and well before they are ' collected together.
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3L~3~9~3 It will be appreciated that the filaments treated in accordance with the process of this invention can be passed directly to a cutting roll to form staple fiber which then is collected for further fiber processing.
It has been found that the very good results were ob-tained when filaments were spun at linear speeds up to 300 meters per minute and that spinning speeds measured at the take-up roll o about 1000 meters per minute or even higher can be used without substantial sticking or fusion of the filaments when collected. However, with a conventional bath, spinning speeds greater than about 200 meters per minute cannot be attained.
It will also be appreciated that any amine oxide composition that will form a solution with cellulose and is compatible with water may be used. Exemplary of some amine oxides are N, N-dimethylcyclohexylamine oxide, dimethylethanol amine oxide, N-methylmorpholine oxide, and dimethyl benzylamine o~ide. The use of amine oxides in processes for dissolving cellulose is disclosed in the patents to Johnson 3,447,939 and 3,508,g41 which particular-ly disclose processes for dissolving celIulose in tertiary amine oxides. Also, the patent to Graenacher 2,179,181 discloses tertiary amines containing 14 or less carbon atoms and discloses that the oxides may be trialkyl amine or an alkylcycloaliphatic tertiary amine. In all cases, however, it has been determined by Applicant's co-workers that the amine oxides require the presence of a critical amount of water in order to dissolve celIulose.
~13S9~L8 The composition of the spinning solution of this invention covers solutions containing from about 1% to about 40% by weight of cellulose, ~rom about 98% to about 50% by weight amine oxicle and from about 20~ to about 1~ by weight of water.
The nonsolvent liquid which has been ~ound to effectively coat the fibers can be water or any suitable aprotic organic liquid which does not react with amine oxide, and is a nonsolvent for cellulose. For example, alcohols having from 1 to 5 carbon atoms may be employed as the nonsolvent, such as methyl alcohol, n-propyl alcohol, isopropyl alcohol and butanol. Also, toluene, xylene, or the like may be employed as the nonsolvent liquid. It has been found that varying amounts of the amine oxide can be incorporated in the nonsolvent liquid; however, the con centration of the amine oxide must be low enough so the character of the liquid remains nonsolvent to cellulose.
In addition, it will be appreciated that mixtures of the compounds that are nonsolvent to cellulose mentioned above ~ay be used as the nonsolvent liauid.
The following examples are exemplary of the processes of this invention and show the conditions and results of applying a coatlng of a nonsolvent liquid to the surface of extruded filaments before they are brought together.
EXAMPLE I
In this example, the extruded filaments were treated in~accordance with the process of this invention ; -17-~3S~
by contacting the surface of the filament against a sur-face containing nonsolvent li~uid.
A spinneret 60 mm in diameter was prepared having thirteen 250-micron(~) holes in two rows, one row had six holes and the other row seven holes~ with the rows staggered, the centerline of each row of holes being 1/8 inch apart and the holes in each row being 1/4 inch apart. A roller applicator was used as the means for applying the nonsolvent liquid to the filaments and was placed at a distance of 27 cm from the spinneret face with the spinneret hole rows running parallel to the turning axis of the roller applicator. l'he point o~
collection was a godet roll 91 cm from the face of the spinneret.
A spinning solution containing 23.8% cellulose, 65.7% amine oxide, and 10.5% H2O was used with the extruding temperature at 120 C at the spinneret level.
An extrusion velocity of 18.76 feet per minute was ~ ;
maintained with a take-up speed of 621 feet per minute, -~
providing a draw ration of 33:1. The extruded filaments ;
were passed over a roller applicator turning at a periphery speed of approximately the speed of the filaments in contact with the roller applicator. The roller appli-cator was immersed in water thus providing a water coating to the surface of the filaments by surface pick- up of ~ -the applicator roll. The filaments were collected over ;
the godet roll and passed onto a spool and the resultant yarn cut in 1-3/4 inch lengths, washed, dried and carded.
The treated yarn carded very well showing that tacking or ~s~
fusing o~ fibers together was subs-tantially eliminated by the surfac~ treatment of the fibers with the nonsolvent liquid.
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EXAMPLE II
The same spinning solulion and process conditions as set forth in Example 1 can be used to make filaments according to the process of the invention except that methanol replaces the nonsolvent liquid applied to the surface of the ~ilaments by the roller applicator.
The resulting filaments are then cut in 1-3/~
inch lengths, washed and dried.
EXAMPLE III
In this Example, a spinning solution similar to that of the above Examples was extruded in the spinning apparatus show in FIGURE 6. After the polymer passes ¦~ ' through a die 12 equipped with a port for pressure or temperature sensing, the polymer is fed to the spinneret 14 by a metering pump 13 having a capacity of 0.58~ cc./min.
The metering pump 13 is surrounded by a bloc~ which can be heated by ~luid flowing therethrough. The extruded filaments were directed downwardly with the nonsol~ent liquid flowing through the tube 91 onto the take-up roll 73.
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EXAMPLE IV
In this Example, the same spinning solution as set forth in Example I was used, the extruded filaments were treated by passing the filaments through a fluid bath of nonsolvent liquid. The filaments extruded were passed through a chamber containing an atmosphere saturated with atomized water particles. The filaments were extruded at a velocity of 4.65 meters per minute (m/min.) and a take-up speed of 207 m/min. giving a draw ration of 44.6:1 with the filaments passing through a chamber containing the atomized water particles for more than 75% of their travel before they were collected. ~he filaments coated with water upon exiting from the chamber were collected together and taken up on a roll. The fibers produced were then cut to form staple fibers of l-3/4 inch lengths, washed and dried.
The dried fibers carded very well showing that the tacking or fusing of fibers during processing was substantially eliminated. The tenacity of the fibers was 2.03 g/denier; the denier was 3O4~ elongation was 9.4~.
It is believed that the coating of the filaments with nonsolvent liquid immediately~after they are extruded helps to retain the orientation developed in the yarn by the drawing and also adds handling strength to the yarn by additional cooling and removal of some of the amine oxide from the solution.
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Although the invention is described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and -that variations can be made therein by those skilled in the art without departing from -the spirit and scope of -the invention except as it may be limited by the claims.
In the process of forming filaments from an extrusion of a cellulose spinning dope, there arises the problem of surface tacking and/or fusion of fila-ments as they are brought in contact with each other at a point of collection. Such tacking and/or fusion of the Eilaments contributes to further difficulties in the continuing processing of -the filaments for their formation into yarn. Of interest in the prior art is the U. S. patent to Blades 3,767,756 which discloses a process for the spinning of filaments from a polyamide spinning dope and passing the filaments through a layer of inert noncoagulating fluid and into a coagulating bath before the filaments are brought together for further processing. Also, the patent to ~organ 3,414,645 is directed to a process for spinning wholly aromatic polyamide fibers in which the filaments after extrusion are passed through gaseous medium for a short distance to evaporate a small amount of the solvent before the fibers enter a coagulation bath, after which they are washed and stretched. None of the art, however, provides for a surface treatment of filaments formed from a solution of cellulose in amine oxide with a surface coating of a nonsolvent liquid that inhibits the fusing and/or tacking of the filaments together when they are collected.
This invention contemplates such a new process ;~
and provides for surface treating filaments extruded from spinning dope of a solution of cellulose dissolved in amine oxide, by applying to the surface of the :, ~
~L~3~ii~1Ei extruded filament, immediately after extrusion, a solu-tion of a nonsolvent liquid capable of rendering the amine oxide inactive as to its abi:Lity to form solutions with cellulose and thus reduce the tendency of tacking and/or fusion of filaments so that when they are collected together, surface tacking or fusing of adjacent filamen-ts is substan-tially reduced.
The coating of the filaments with the nonsolvent may be accomplished by passing them immediately after extrusion and before they are collected together into ~.
contact wi-th a surface that contains a continuous supply of a liquid which is nonsolvent for cellulose so that the surface of the filaments is continually coated with the nonsolvent liquid.
In addition to sur~ace coating of the filaments with the nonsolvent liquid, the surface of the filaments can be passed through a chamber having nonsolvent vapor laden atmosphere, such as a fog of minute particles or droplets of nonsolvent liquid, so that particles of the nonsolvent liquid are deposited on the surface of the filaments. In order to increase the deposition of the liquid particles on the surface of the extruded fila-ments an electrostatic charge can be placed on the filaments such that the surface of the filaments has a polarity opposite to that of the particles in the vapor laden atmosphere thereby increasing the attraction of the particles to the surface of the filaments.
Another method by which the extruded filaments may be coated with the nonsolvent liquid is by passing the filaments as extruded through a vapor layer of non-solvent liquid for a very short period of time and then ~3~L8 into a tank which contains the nonsolvent liquid, and then bringing the coated filaments together.
Still another method for coating the filam0nts with nonsolvent liquid is by extrusion of the filaments through a spinneret in which a plurality of jet openings, communicating with a chamber providing a continuous supply of nonsolvent liquid, are positioned adjacent to the spinneret orifices. By passing a nonsolvent liquid -through the jet openings in the spinneret as the fila-ments are extruded through the spinneret orifices, the surface of each filamen-t is immediately, or after a very short interval of contact with air in a gap between the spinneret orifices and the nonsolvent liquid, coated with nonsolvent liquid, thus preventing tacking or fusing of ~-filaments when they are brought together.
The extruded filaments of this invention can be ~-subjected to a drawing operation during the application of the nonsolvent with a major portion of the drawing of the filaments to induce improved physical properties therein being accomplished before the nonsolvent liquid coated filaments are collected together. Extruded filaments treated in accordance with the process of this invention, after being coated with the nonsolvent liquid, can be handled by conventional wet spinning equipment~
These and other objects will become apparent from the following description of the preferred embodiments `~-and examples and the accompanying drawings which illus-trate diagrammatically an apparatus which may be used to practice the process of this invention, in which drawings:
~ :;
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,' ~l~13S9~
FIGURE 1 is a schematlc view of an apparatus for carrying out the process of the invention, in which a nonsolvent liquid is applied to the filaments by a roller applicator;
F~GURE 2 is a schematic view of a modification of the roller applicator in FIGURE 1 showing spaced concentric grooves with filaments contacting the surface of the grooves in the surface of the roller applicator;
F~GURE 3 is a schematic view of a modification of FTGURE 1 in which the nonsolvent liquid is applied to the fila-ments by contact with the edge of a plate surface supportinga film of nonsolvent liquid;
FIGURE 4 is a schematic view of a modification of FIGURE 3 in which the plate has an annular~shaped contact sur-face containing a film of a nonsolvent liquid;
FIGURE 5 is a schematic view of a further embodiment o~ the invention showing an apparatus for applying nonsolvent liquid to the surface of the filaments passing through a cham-ber COntainLng aerosolized or atomized nonsolvent particles;
F~GURE 6 is a schematic view of still another embodi-~2Q ment of the invention showing an apparatus for applying non-solvent liquid to the surface of filaments as the filarnents pass through a vertical tube with nonsolvent liquid flowing ,:
through it; and F~GURE 7 is a schematic view of still a further embodi- 1 .
ment of the invention showing nonsolvent liquid flowing through jet openings in a spinneret plate adjacent to spinneret ori-fices and is located on the same sheet as FIGURE 1;
FIGURE 8 is a schematic view of stiIl another .
.
j~
~ _ 5 _ ~13~
embodiment of the invention showing an appartus for applying nonsolvent liquid to -the surface of filaments passing through a chamber containlng foamed nonsolvent liquid and is located on the same sheet as Figure 2.
In FIGURE 1 is illustrated the applying of a nonsolvent liquid to the surface of a spun filament formed from cellulose dissolved in amine oxide in accordance with this invention. The solution of cellulose in amine oxide can be made in a conventional manner, e.g. t by dissolving cellulose in an amine oxide solution in a heated tank, preferably under pressure or by any other means. For example, as illus-trated, solid cellulose sheets impregnated with the amine oxide solvent are added to a hopper and fed by an extruder 11 through a die port 12 to a metering b device 13 whereby the cellulose becomes completely dissolved in the amine oxide at the elevated temperature `~
and pressure in the extruder, then extruded or spun through a spinneret 14.
The use of an extruder to dissolve amine oxide-impregnated cellulose is more fully described in U.S. Patent No. 4,144,080.
The cellulose solution is continuously extruded from the spinneret 14 to form a plurality of filaments 15 which, due to the amount of tertiary amine oxide solvent present in their composition, must be carefully spaced from each other so that sticking or fusion of the filaments does !`
f t,~
. .
~59~
not occur. To accomplish this, the spinneret orifices are patterned so that the extruded filaments remain spaced from one another until they are collected together for further processing. The filaments 15 pass downward through a small air space 16 in which some of the volatile solvent from the surface of the filaments is removed. All filaments are ext:ruded so that in their downward travel they contact a portion of the surface of an applicator roll 17 which can be driven at any speed in either direction, but preferably rotates in the same direction and at a peripheral speed less than the linear speed of the filaments to reduce the tendency of the filaments to fuse together. The rotating applicator roll 17 is positioned with its bottom portion imm2rsed in a trough 18 containing the nonsolvent liquid so that its surface maintains a constant supply of nonsolvent liquid for the coating in the filaments passing against its surface. Nonsolvent liquid is supplied to trough 18 from a supply tank 19 by a pump 20 to maintain a constant supply of nonsolvent liquid in trough 18. It will be appreciated that the surface of the applicator roll must be formed from a material that is capable of the proper degree of liquid pick-up so that its surface continuously presents an amount of liquid that will effectively coat the surface of the filaments when they are brought into contact with the surface o the applicator roll.
AEter the coating of the filaments with the nonsolvent liquid, they are brought together and passed around a turn:Lng godet roll 21 and then between feed rolls 22 to take-up roll 23. The filaments before ~, ~
:. ~ . : , . i .-. .. . . .. .
- ~35~
collection ancl passing over the godet 21 have their surface coated with a thin film of a nonsolvent which substantially eliminates tacking and/or fusing of adjacent filaments.
Advantageously, the surface of -the roller applicator 17 may have concentric spaced surface grooves 24 positioned so that individual filaments 15 can be guided during their contact with applicator roll 17.
It will be appreciated that the individual grooves 24 not only assist in maintaining filaments at a desired spaced interval from each other but also provide in the grooves a pool of nonsolvent liquid which assists in the efficiency of application of the nonsolvent liquid to the surface of the filaments, requiring less contact time in which the surface of the filaments must be in contact with the surface of the applicator roll 17 (see FIGURE 2).
It will be appreciated that in the roller appli-cation of the nonsolvent, the filaments can be directed so that the surface of the spaced filaments just kiss the surface of the roller applicator or can be brought into contact so that they maintain a contact with the roller surface over a segment of the surface. The amount of contact, of course, will depend on the ability of the surface of the applicator roll to pick up nonsolvent liquid and impart it to the surface of the filaments. It is important that the applicator roll have a pick-up surface that will not abrade or break the thread line while possessing the ability to pick up sufficient liquid and deposit it effectively on the surface of the filament during the period of contact.
. , .. , ; ,, . ~ .. . - , . ~ .. . . . . .
" ~35~
The roller applicator may be rotated in either direction, but when the roller applicator 17 is rotated in the same direction as the ~ilament travels, as illus-trated in FIGURE 2, at the point of tangency where the filament fi~st contacts the surface, the peripheral speed of the roller preferably should be less than the linear speed of the filament. In either case, the peripheral speed of the roller should be not less ~han a speed that will carry a sufficient amount o~ nonsolvent liquid to coat the filaments.
~ t will also be appreciated that the nonsolvent liquid can be applied to the roller applicator surface as by other means than by immersion of the applicator such as by spray nozzles or a doctor blade in which the liquid can be sprayed or doctored onto the surface of the roller to provide the desired amount of liquid to be applied to the surface of the filaments.
Another method of contact application of the nonsolvent liquid to the surface of the filaments is shown in FIGURE 3 in which the filaments 15 are brought into contact with a curved edge 28 or a plate 26 which has a downwardly tilted surface that terminates in the curved edge 28. Positioned in the surface of the plate applicator is a series of spaced outlets 30 through which continuously flows nonsolvent liquid that passes over the surface of th~ plates and then passes over the cur~ed edge so that the filaments 15 continuously contact the edge 28 where they are coated with the nonsolvent liquid.
~3~i9~l~
The outlets 30 are operatively connected to a supply line 31 through which the nonsolvent liquid is continuously supplied to the outlets by a pump 32 from a supply source 33 located under the applicator plate 26.
The nonsolvent liquid passing over edge 28 is collected in supply source 33 where it is recycled to the plate 26.
Another method of application of a nonsolvent liquid to the surface of the extruded filaments is shown in FIGURE 4 in which a donut-shaped applicator sur~ace 40 is used to apply the nonsolvent liquid to the extruded filaments. The filaments 15 are passed in contact with inner annular surface 41. ~he top of the donut-shaped applicator 40 has a series of spaced holes 43 which are operatively connected to a supply line 44 having a metering pump 45 which supplies a con-stant flow of nonsolvent liquid to the top surface of the donut-shaped applicator from a supply source 45, which is positioned under a godet roll 47 which is the point of collection of the filaments that have been coated with the liquid. The collected filaments from godet roll 47 are turned and passed through feed rolls 48, 48A and then to a take-up roll 49. The liquid after flowing over the inner annular surface 41 is coltected at the supply source. The position of the holes 43 is .. .
on the downward side of the top of the curved surface that forms the inner annular surface so that the liquid will flow towards and over this surface to supply the required amount of nonsolvent liquid to the filaments.
The direction of the liquid could be reversed so the . - ~
~3L3S~
liquid travels to -the outside edge of the donut, and the filaments are maintained in con-tact with the outside, rounded edge of the donut. Similarly, a flat horizontal circular plate with rounded edges can be used for applying nonsolvent li~uid to -the surEace of the filaments. It will be appreciated that in all plate applicator con-structions, the extruded filaments contact the edge of the plate and the spinneret orifices are patterned so that the filaments will be extruded so that their thread line will not make contact with each other until after the nonsolvent liquid has been applied.
It also will be appreciated that the spinning solution must have sufficient viscosity so that fila-ments formed from it will be able to withstand any forces that may be present during the period of contact with the applicator surface so that there is no breaking of the thread line. One skilled in spinning will be able to adjust the condition, i.e., spinning velocity~ the position of the applicator and the take-up speed, concentration of amine oxide in the spin bath to obtain a fiber of the desired denier and physical properties.
FIGURE 5 is another embodiment of the process ;
of the invention. In this embodiment a hopper 10 supplies solid cellulose and amine oxide solvent or 25 cellulose impregnated with amine oxide solvent to an extruder 11 which mixes the materials and where a solution is formed as previously mentioned and conveyed to a metering device 13. The metering device 13, which may be a pump, conveys a metered amount of the solution 30 through spinneret 14 to form continuously extruded . - ~ - ~ -. . . ..
~3~ ~ ~ ~
filaments 15. The ~ilaments 15 pass from the spinneret into the top of a fog chamber 51 containing an atmosphere laden with particles of nonsolvent liquid. The filaments pass through the fog chamber 51 into a lower chamber 52 where they are collected on a take-up roll 53 or further processed, e.g., cut into staple, washed, etc.
During their passage through the fog chamber, the particles of nonsolvent liquid are condensed onto the surface of the filaments to inactivate the solvent so as to cause precipitation of the cellulose on the surEace of the filaments, thus eliminating the tackiness at the surface and tendency of filaments to stick to each other. Nonsolvent liquid is collected in the lower "~ ~
chamber 52 and is recirculated by a pump means 54 through a liquid line 55 into the chamber 51 through an atomizing nozzle 56 positioned in the chamber 51.
Positioned in the lower chamber 52 is an outlet opening 57 for removal of air laden with nonsolvent liquid which is passed through a condenser means 59 with the air free of nonsolvent liquid exiting through opening 60 to the atmosphere and the condensed nonsolvent liquid passing through line 61 to pump means 54 where it ~-is recycled to atomizing nozzle 56.
~dvantageously, the fog chamber 51 may have more than one atomizing nozzle 56 spaced so that the fog chamber is provided with a substantially uniform atmos-phere laden with nonsolvent liquid particles to aid in ;-covering of the surface of the filaments with nonsolvent -liquid as the filaments travel from the spinneret to their -point of collection on the take-up roll.
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It will be appreciated -that the aerosolized or atomized nonsolvent particles must be rather small and must be introduced into the fog producing chamber in a manner so that there is a minimum of turhulance to prevent the filaments passing downwardly through the atomized particles from beiny swayed from their normal path.
Also, the concentration of suspended nonsolvent particles in the atmosphere must be sufficient so that the surface of all the filaments passing through the chamber 51 have atomized particles of nonsolvent deposited during substantially all of their travel through the cha~ber 51.
Advantageously, the extruded filaments may be electrically ¦
charged so t}iat the surface of the filament will attract suspended particles of li~uid. Suitable control means 62 can be provided to assure that the pressure in line 55 is maintained so that the proper quantity of nonsolvent liquid is passed through the nozzles to produce the desired atmosphere.
FIGURE 6 of the drawings shows a still further embodiment of the process of this invention. In this embodiment the filaments 15 are extruded from spinneret 14 through a small air space 16 and into an immersion tank 70 containing nonsolvent liquid. Exiting from the bottom -of immersion tank 70 is a downwardly extended tube 91 which exits into a lower tank 92. Connected to the bottom portion of tank 92 is a liquid supply line 75 which by pump means 74 transfers nonsolvent Iiquid ~rom lower tank 92 to immersion tank 70. The pump means 74 maintains a constant flow of nonsolvent from the lower tank 92 to immersion tank 70 to maintain the level in . . . i . . . , - ~ . ~ , . . .
~3~9~L~
the immersion tank constant, thus xeplacing nonsolvent liquid that flows downward through vertical tube 91.
The filaments pass through the nonsolvent liquid in the ~mmersion tank and the extended tube 91 and pass over take-up rolls 95 where they are cut into staple fibers which are collected and removed for further fiber processing.
In air space 16 is maintained a constant vapor layer which may consist of an inert gas or a nonsolvent vapor or fog between the spinneret and the surface of the liquid in the immersion tank 70. It has been found that excellent results are o~tained when the gaseous or vapor layer through which the filaments pass is from about 0.5 cm to greater than 10 cm in length, F~GURE 7 of the drawings illustrates another embodi-ment of the invention in which the nonsolvent liquid is sprayed directly into the downward path of extruded filaments as they are formed. In this process the nonsolvent liquid is sprayed from ~ plurality of openings 90 in the face of the spinneret 14 pos~tioned adjacent to spinneret orifices. The filaments covered with nonsolvent liquid travel downwardly to a godet roll 71 where the filaments are collected and turned and pass ¦
through a pair of feed rolls 72, 72A to a take-up roll 73. ¦
The open~ngs 90 in the spinneret communicate with a supply of nonsolvent liquid which is ~orced through the opening ~y pump 74 hrough a supply line 75 2rom a supply ¦
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of nonsolvent liquid in a container 76. The sprayed non-solvent liquid which does not adhere -to the surface of the filaments falls by gravity into t.he container 76. The pump 74 maintains sufficient pressure in the liquid line 75 to assure that the proper quantity of nonsolvent liquid is spray-ed throuyh the opening 90 to provide jets of liquid that will effectively cover the surface of the extruded filaments before they arebrouyht together.
F~URE 8 is similar to FIGU~E 7 and the same numerals are used Eor like features. In FIGURE 8, the filaments are extruded or spun through the spinneret 1~ into a chamber 80 having an inlet 81 and an outlet 82 for the introduction of the nonsolvent and a foamy carrier, such as a surfactant, which can be foamed easily in mixing vessel 83 by mixing with the nonsolvent liquid and can easily be separated from the nonsolvent liquid. l'he foamy carrier provides for rapid and complete contact of the'~ilament as it leaves the spinneret by the'nonsolvent liquid. The preferred foamy carrier sur~
factant may be a nonionic surfactant such as ethoxylated fatty alcohols, ethoxylated fatty acids or ethoxylated(s) alkyl phenols or long-chain amine oxides, e.g., dimethyl coco amine , oxide, N-coco morpholine oxide.
During the application of the nonsolvent, the fila- ' ments can be drawn with a draw ratio of from 1:1 to about -1:100 with a major portion of the filament drawin~ being performed close to the spinneret and well before they are ' collected together.
' :
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3L~3~9~3 It will be appreciated that the filaments treated in accordance with the process of this invention can be passed directly to a cutting roll to form staple fiber which then is collected for further fiber processing.
It has been found that the very good results were ob-tained when filaments were spun at linear speeds up to 300 meters per minute and that spinning speeds measured at the take-up roll o about 1000 meters per minute or even higher can be used without substantial sticking or fusion of the filaments when collected. However, with a conventional bath, spinning speeds greater than about 200 meters per minute cannot be attained.
It will also be appreciated that any amine oxide composition that will form a solution with cellulose and is compatible with water may be used. Exemplary of some amine oxides are N, N-dimethylcyclohexylamine oxide, dimethylethanol amine oxide, N-methylmorpholine oxide, and dimethyl benzylamine o~ide. The use of amine oxides in processes for dissolving cellulose is disclosed in the patents to Johnson 3,447,939 and 3,508,g41 which particular-ly disclose processes for dissolving celIulose in tertiary amine oxides. Also, the patent to Graenacher 2,179,181 discloses tertiary amines containing 14 or less carbon atoms and discloses that the oxides may be trialkyl amine or an alkylcycloaliphatic tertiary amine. In all cases, however, it has been determined by Applicant's co-workers that the amine oxides require the presence of a critical amount of water in order to dissolve celIulose.
~13S9~L8 The composition of the spinning solution of this invention covers solutions containing from about 1% to about 40% by weight of cellulose, ~rom about 98% to about 50% by weight amine oxicle and from about 20~ to about 1~ by weight of water.
The nonsolvent liquid which has been ~ound to effectively coat the fibers can be water or any suitable aprotic organic liquid which does not react with amine oxide, and is a nonsolvent for cellulose. For example, alcohols having from 1 to 5 carbon atoms may be employed as the nonsolvent, such as methyl alcohol, n-propyl alcohol, isopropyl alcohol and butanol. Also, toluene, xylene, or the like may be employed as the nonsolvent liquid. It has been found that varying amounts of the amine oxide can be incorporated in the nonsolvent liquid; however, the con centration of the amine oxide must be low enough so the character of the liquid remains nonsolvent to cellulose.
In addition, it will be appreciated that mixtures of the compounds that are nonsolvent to cellulose mentioned above ~ay be used as the nonsolvent liauid.
The following examples are exemplary of the processes of this invention and show the conditions and results of applying a coatlng of a nonsolvent liquid to the surface of extruded filaments before they are brought together.
EXAMPLE I
In this example, the extruded filaments were treated in~accordance with the process of this invention ; -17-~3S~
by contacting the surface of the filament against a sur-face containing nonsolvent li~uid.
A spinneret 60 mm in diameter was prepared having thirteen 250-micron(~) holes in two rows, one row had six holes and the other row seven holes~ with the rows staggered, the centerline of each row of holes being 1/8 inch apart and the holes in each row being 1/4 inch apart. A roller applicator was used as the means for applying the nonsolvent liquid to the filaments and was placed at a distance of 27 cm from the spinneret face with the spinneret hole rows running parallel to the turning axis of the roller applicator. l'he point o~
collection was a godet roll 91 cm from the face of the spinneret.
A spinning solution containing 23.8% cellulose, 65.7% amine oxide, and 10.5% H2O was used with the extruding temperature at 120 C at the spinneret level.
An extrusion velocity of 18.76 feet per minute was ~ ;
maintained with a take-up speed of 621 feet per minute, -~
providing a draw ration of 33:1. The extruded filaments ;
were passed over a roller applicator turning at a periphery speed of approximately the speed of the filaments in contact with the roller applicator. The roller appli-cator was immersed in water thus providing a water coating to the surface of the filaments by surface pick- up of ~ -the applicator roll. The filaments were collected over ;
the godet roll and passed onto a spool and the resultant yarn cut in 1-3/4 inch lengths, washed, dried and carded.
The treated yarn carded very well showing that tacking or ~s~
fusing o~ fibers together was subs-tantially eliminated by the surfac~ treatment of the fibers with the nonsolvent liquid.
!
EXAMPLE II
The same spinning solulion and process conditions as set forth in Example 1 can be used to make filaments according to the process of the invention except that methanol replaces the nonsolvent liquid applied to the surface of the ~ilaments by the roller applicator.
The resulting filaments are then cut in 1-3/~
inch lengths, washed and dried.
EXAMPLE III
In this Example, a spinning solution similar to that of the above Examples was extruded in the spinning apparatus show in FIGURE 6. After the polymer passes ¦~ ' through a die 12 equipped with a port for pressure or temperature sensing, the polymer is fed to the spinneret 14 by a metering pump 13 having a capacity of 0.58~ cc./min.
The metering pump 13 is surrounded by a bloc~ which can be heated by ~luid flowing therethrough. The extruded filaments were directed downwardly with the nonsol~ent liquid flowing through the tube 91 onto the take-up roll 73.
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EXAMPLE IV
In this Example, the same spinning solution as set forth in Example I was used, the extruded filaments were treated by passing the filaments through a fluid bath of nonsolvent liquid. The filaments extruded were passed through a chamber containing an atmosphere saturated with atomized water particles. The filaments were extruded at a velocity of 4.65 meters per minute (m/min.) and a take-up speed of 207 m/min. giving a draw ration of 44.6:1 with the filaments passing through a chamber containing the atomized water particles for more than 75% of their travel before they were collected. ~he filaments coated with water upon exiting from the chamber were collected together and taken up on a roll. The fibers produced were then cut to form staple fibers of l-3/4 inch lengths, washed and dried.
The dried fibers carded very well showing that the tacking or fusing of fibers during processing was substantially eliminated. The tenacity of the fibers was 2.03 g/denier; the denier was 3O4~ elongation was 9.4~.
It is believed that the coating of the filaments with nonsolvent liquid immediately~after they are extruded helps to retain the orientation developed in the yarn by the drawing and also adds handling strength to the yarn by additional cooling and removal of some of the amine oxide from the solution.
; -20-.. . ... . ..
~3~
Although the invention is described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and -that variations can be made therein by those skilled in the art without departing from -the spirit and scope of -the invention except as it may be limited by the claims.
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for inhibiting surface adhesion of adjacent filaments formed from a spinning of a solution contain-ing cellulose in amine oxide comprising: continuously extrud-ing said spinning solution to form spaced adjacently position-ed filaments and, before said filaments are brought into contact with each other, applying to the surface of said filaments a continuous coating of a nonsolvent liquid that will reduce the solvent action of the amine oxide for cellulose at the surface of the filaments.
2. The process of Claim l in which said spinning solution is a solution of cellulose in amine oxide comprising from about 1% to about 40% by weight cellulose, from about 98%
to about 50% by weight amine oxide, and from about 20% to about 1% water.
to about 50% by weight amine oxide, and from about 20% to about 1% water.
3. The process of Claim 1 in which the non-solvent liquid that will reduce the solvent action of the amine oxide for cellulose is a sterically unhindered aprotic compound or mixture thereof selected from the group consisting of low molecular weight alcohols, organic acids, dilute mineral acids and water.
4. The process of Claim 1 in which the non-solvent liquid that will reduce the solvent action of the amine oxide for cellulose is water.
5. The process of Claim 3 in which the aprotic liquid is an alcohol having from one to about five carbon atoms.
6. The process of Claim 1 in which the fila-ments are subjected to drawing immediately after extrusion to improve their physical properties with at least the major portion of the draw of the filaments being done before said filaments are brought together.
7. The process of Claim 6 in which the ratio of draw of said filaments is from 1:1 to about 1:100.
8. The process of Claim 1 in which the filaments after said nonsolvent liquid has been applied are collected and passed over a cutter roll to produce cut staple fibers.
9. The process of Claim 1 in which the filaments after said nonsolvent liquid has been applied are collected onto a take-up roll.
10. The process of Claim 1 in which the surface of said filaments is coated with said nonsolvent liquid by contact with an applicator surface containing a film of the nonsolvent liquid.
11. The process of Claim 10 in which the ap-plicator surface is a rotating cylinder with a nonsolvent liquid continuously supplied to its surface.
12. The process of Claim 11 in which the sur-face of said rotating cylinder has a peripheral speed sub-stantially less than the linear speed of said filaments.
13. The process of Claim 11 in which the sur-face of said rotating cylinder has a plurality of spaced grooves encircling its peripheral surface with each filament riding in one of said grooves for a portion of the periphery continuously in contact with the nonsolvent liquid in the grooves.
14. The process of Claim 10 in which the applicator surface is a stationary flat plat having a curved edge over which continuously flows the nonsolvent liquid with the filaments contacting the nonsolvent liquid as it flows over the edge of the plate.
15. The process of Claim 10 in which the appli-cator surface is of stationary circular construction having downwardly positioned curved edges with nonsolvent liquid continuously flowing over said downwardly positioned curved edges with said filaments contacting the nonsolvent liquid flowing over said edges.
16. The process of Claim 15 in which said applicator of circular construction is donut-shaped having nonsolvent liquid flowing over at least one inner or outer annular surface having a pattern of spinneret orifices posi-tioned to direct the extruded filaments over the said down-wardly positioned curved edges without contacting one another.
17. The process of Claim 1 in which said fila-ments are passed through an atmosphere containing said non-solvent liquid particles to deposit the coating of said non-solvent liquid on the surface of said filaments.
18. The process of Claim 17 in which said filaments have an induced electrical charge to attract particles of nonsolvent liquid onto the surface of said filaments to increase the deposition of said nonsolvent liquid.
19. The process of Claim 1 in which a spray of said nonsolvent liquid is applied to the surface of said fila-ments as the filaments are being extruded.
20. The process of Claim 1 in which said fila-ments are extruded from a spinneret head that has holes which directs said nonsolvent liquid onto the surface of said fila-ments.
21. The process of Claim 1 in which a foam com-prising said nonsolvent liquid and a foamable surfactant is applied to said filaments.
22 The process of Claim 1 in which the fila-ments are passed through a chamber containing a foam comprising said nonsolvent liquid.
23. The method for making a cellulose fiber which comprises spinning into an air space a solution containing cellulose dissolved in a tertiary amine oxide solvent for cellulose, drawing the resulting filaments in an inert gas while avoiding mutual contact to orient their molecular structure, wetting the surface of said filaments with a nonsolvent for cellulose which is compatible with said solution to precipitate cellulose only adjacent to the surface of the filaments about a core of said solution, precipitating the cellulose in said core with nonsolvent for the cellulose, and drying the resulting fiber without additional drawing.
24. The process of Claim 23 wherein the inert gas is air.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84720077A | 1977-10-31 | 1977-10-31 | |
| US847,200 | 1977-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1135918A true CA1135918A (en) | 1982-11-23 |
Family
ID=25300046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000314744A Expired CA1135918A (en) | 1977-10-31 | 1978-10-30 | Process for surface treating cellulose products |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS5473919A (en) |
| AT (1) | AT365663B (en) |
| AU (1) | AU4066878A (en) |
| BE (1) | BE871428A (en) |
| CA (1) | CA1135918A (en) |
| DD (1) | DD139733A5 (en) |
| DE (1) | DE2844163C3 (en) |
| DK (1) | DK482678A (en) |
| ES (1) | ES474668A1 (en) |
| FI (1) | FI64660C (en) |
| FR (1) | FR2407280A1 (en) |
| GB (1) | GB2007147B (en) |
| IN (1) | IN150036B (en) |
| IT (1) | IT1196397B (en) |
| NL (1) | NL7810788A (en) |
| NO (1) | NO783646L (en) |
| RO (1) | RO85081B (en) |
| SE (1) | SE451856B (en) |
| ZA (1) | ZA785535B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5607639A (en) * | 1993-09-13 | 1997-03-04 | Lenzing Aktiengesellschaft | Process for the preparation of cellulose sheet |
| US5650112A (en) * | 1993-07-28 | 1997-07-22 | Lenzing Aktiengesellschaft | Process of making cellulose fibers |
| US11873580B2 (en) | 2018-12-28 | 2024-01-16 | Lenzing Aktiengesellschaft | Process for liquid removal from cellulose filaments yarns or fibers |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246221A (en) * | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
| DE3729062A1 (en) * | 1987-08-31 | 1989-03-09 | Hoechst Ag | METHOD FOR PRODUCING PREPARATION-FREE STRETCHED FIBERS |
| US5520869A (en) * | 1990-10-12 | 1996-05-28 | Courtaulds Plc | Treatment of fibre |
| GB9022175D0 (en) * | 1990-10-12 | 1990-11-28 | Courtaulds Plc | Treatment of fibres |
| AT395863B (en) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
| GB9103297D0 (en) * | 1991-02-15 | 1991-04-03 | Courtaulds Plc | Fibre production method |
| ATA53792A (en) * | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
| US5882356A (en) * | 1992-10-21 | 1999-03-16 | Courtaulds Fibres (Holdings) Limited | Fibre treatment |
| GB9304887D0 (en) * | 1993-03-10 | 1993-04-28 | Courtaulds Plc | Fibre treatment |
| TR28441A (en) * | 1993-05-24 | 1996-07-04 | Courtaulds Fibres Holdings Ltd | Spinning cells that can be used to coagulate lyocell filaments. |
| AT399729B (en) * | 1993-07-01 | 1995-07-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FIBERS AND DEVICE FOR IMPLEMENTING THE METHOD AND THE USE THEREOF |
| GB9407496D0 (en) * | 1994-04-15 | 1994-06-08 | Courtaulds Fibres Holdings Ltd | Fibre treatment |
| GB9408742D0 (en) * | 1994-05-03 | 1994-06-22 | Courtaulds Fibres Holdings Ltd | Fabric treatment |
| GB9410912D0 (en) * | 1994-06-01 | 1994-07-20 | Courtaulds Plc | Fibre treatment |
| US6165401A (en) * | 1997-04-25 | 2000-12-26 | Lenzing Aktiengesellschaft | Process for the production of cellulosic moulded bodies |
| BR9804868A (en) * | 1997-04-25 | 1999-08-24 | Chemiefaser Lenzing Ag | Process for the production of molded cellulose bodies |
| AT404731B (en) | 1997-04-25 | 1999-02-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FLAT FILMS AND THEIR USE |
| AT404846B (en) | 1997-06-16 | 1999-03-25 | Chemiefaser Lenzing Ag | COMPOSITION CONTAINING FINE SOLID PARTICLES |
| DE19954152C2 (en) * | 1999-11-10 | 2001-08-09 | Thueringisches Inst Textil | Method and device for producing cellulose fibers and cellulose filament yarns |
| DE10200405A1 (en) | 2002-01-08 | 2002-08-01 | Zimmer Ag | Cooling blowing spinning apparatus and process |
| DE10206089A1 (en) | 2002-02-13 | 2002-08-14 | Zimmer Ag | bursting |
| DE102004024030A1 (en) | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell process with polymerization-degree-dependent adjustment of the processing time |
| US8479897B2 (en) | 2009-07-06 | 2013-07-09 | Shimano Inc. | Bolt for hydraulic disc brake caliper |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3415922A (en) * | 1965-07-02 | 1968-12-10 | Monsanto Co | Mist spinning |
| US3447939A (en) * | 1966-09-02 | 1969-06-03 | Eastman Kodak Co | Compounds dissolved in cyclic amine oxides |
| US3767756A (en) * | 1972-06-30 | 1973-10-23 | Du Pont | Dry jet wet spinning process |
-
1978
- 1978-09-29 ZA ZA00785535A patent/ZA785535B/en unknown
- 1978-10-10 DE DE2844163A patent/DE2844163C3/en not_active Expired
- 1978-10-12 AU AU40668/78A patent/AU4066878A/en active Pending
- 1978-10-20 BE BE191257A patent/BE871428A/en not_active IP Right Cessation
- 1978-10-30 ES ES474668A patent/ES474668A1/en not_active Expired
- 1978-10-30 SE SE7811241A patent/SE451856B/en not_active IP Right Cessation
- 1978-10-30 NO NO783646A patent/NO783646L/en unknown
- 1978-10-30 DK DK482678A patent/DK482678A/en unknown
- 1978-10-30 IN IN780/DEL/78A patent/IN150036B/en unknown
- 1978-10-30 CA CA000314744A patent/CA1135918A/en not_active Expired
- 1978-10-30 RO RO95542A patent/RO85081B/en unknown
- 1978-10-30 GB GB7842475A patent/GB2007147B/en not_active Expired
- 1978-10-30 FI FI783295A patent/FI64660C/en not_active IP Right Cessation
- 1978-10-30 DD DD78208764A patent/DD139733A5/en unknown
- 1978-10-30 IT IT29233/78A patent/IT1196397B/en active
- 1978-10-30 NL NL7810788A patent/NL7810788A/en not_active Application Discontinuation
- 1978-10-30 JP JP13441578A patent/JPS5473919A/en active Granted
- 1978-10-30 AT AT0774078A patent/AT365663B/en not_active IP Right Cessation
- 1978-10-30 FR FR7830743A patent/FR2407280A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650112A (en) * | 1993-07-28 | 1997-07-22 | Lenzing Aktiengesellschaft | Process of making cellulose fibers |
| US5607639A (en) * | 1993-09-13 | 1997-03-04 | Lenzing Aktiengesellschaft | Process for the preparation of cellulose sheet |
| US11873580B2 (en) | 2018-12-28 | 2024-01-16 | Lenzing Aktiengesellschaft | Process for liquid removal from cellulose filaments yarns or fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2007147B (en) | 1982-03-03 |
| JPS5473919A (en) | 1979-06-13 |
| FI64660C (en) | 1983-12-12 |
| IT1196397B (en) | 1988-11-16 |
| IN150036B (en) | 1982-07-03 |
| DE2844163A1 (en) | 1979-05-03 |
| FI64660B (en) | 1983-08-31 |
| ZA785535B (en) | 1979-09-26 |
| NO783646L (en) | 1979-05-02 |
| RO85081B (en) | 1984-11-30 |
| ATA774078A (en) | 1981-06-15 |
| AU4066878A (en) | 1980-04-17 |
| FR2407280A1 (en) | 1979-05-25 |
| SE451856B (en) | 1987-11-02 |
| GB2007147A (en) | 1979-05-16 |
| NL7810788A (en) | 1979-05-02 |
| DE2844163C3 (en) | 1981-04-16 |
| DE2844163B2 (en) | 1980-07-31 |
| BE871428A (en) | 1979-04-20 |
| DK482678A (en) | 1979-05-01 |
| JPS5749656B2 (en) | 1982-10-23 |
| AT365663B (en) | 1982-02-10 |
| DD139733A5 (en) | 1980-01-16 |
| FI783295A (en) | 1979-05-01 |
| IT7829233A0 (en) | 1978-10-30 |
| SE7811241L (en) | 1979-05-01 |
| ES474668A1 (en) | 1979-03-16 |
| RO85081A (en) | 1984-10-31 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |