US2962341A - Viscose modification - Google Patents
Viscose modification Download PDFInfo
- Publication number
- US2962341A US2962341A US584450A US58445056A US2962341A US 2962341 A US2962341 A US 2962341A US 584450 A US584450 A US 584450A US 58445056 A US58445056 A US 58445056A US 2962341 A US2962341 A US 2962341A
- Authority
- US
- United States
- Prior art keywords
- viscose
- bath
- yarn
- gel
- ether
- 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 - Lifetime
Links
- 229920000297 Rayon Polymers 0.000 title claims description 70
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 19
- 239000004627 regenerated cellulose Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 206010042674 Swelling Diseases 0.000 description 37
- 230000008961 swelling Effects 0.000 description 36
- 239000003607 modifier Substances 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 229920002678 cellulose Polymers 0.000 description 20
- 239000001913 cellulose Substances 0.000 description 20
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 17
- 230000001112 coagulating effect Effects 0.000 description 16
- 238000009987 spinning Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 8
- 229960001763 zinc sulfate Drugs 0.000 description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229960005323 phenoxyethanol Drugs 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012991 xanthate Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000001143 conditioned effect Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- JMYBSSVCXVQZFN-UHFFFAOYSA-N 1-(2-phenoxyethoxy)ethanol Chemical compound CC(O)OCCOC1=CC=CC=C1 JMYBSSVCXVQZFN-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- SXYRTDICSOVQNZ-UHFFFAOYSA-N 1-(2-methoxyethoxy)ethanol Chemical compound COCCOC(C)O SXYRTDICSOVQNZ-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 3
- -1 ether ethanols Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- AGYUOJIYYGGHKV-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)ethane Chemical compound ClCCOCCOCCCl AGYUOJIYYGGHKV-UHFFFAOYSA-N 0.000 description 1
- KWWMSEBBFCCRRA-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOC(C)O KWWMSEBBFCCRRA-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USAIOOFEIMNEDN-UHFFFAOYSA-L disodium;carbonotrithioate Chemical compound [Na+].[Na+].[S-]C([S-])=S USAIOOFEIMNEDN-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XDCZBGLKMJMACF-UHFFFAOYSA-N ethanol Chemical compound CCO.CCO.CCO XDCZBGLKMJMACF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
Definitions
- This invention relates to the production of improved regenerated cellulose structures and especially filaments, yarns, cords and the like having improved physical properties. More particularly, the invention relates to the reduction of the primary swelling of gel :fila'ments from viscose with substantial improvement in filament and yarn properties.
- An object of this invention is to provide new and effective modifiers for viscose which -will .permit the manufacture of regenerated cellulose filaments, yarns, cords and the like exhibiting considerably improvediproperties as compared with filamentous products produced from unmodified viscose.
- Another object of the invention is to provide a yarn manufacturing process from modified viscose which yields filaments having low gel swelling values, high tenacity and a high proportion of skin.
- R is alkyl or-aryl
- n is 'aniritegerof from 1 to 4, inclusive, and R is hydrogen, alkyl or 'aryl; and extruding the resultant viscose into an acid coagulating bath which preferably contains up to Zinc sulfate.
- the coagulated filaments or the like are subjected to the action of a secondary hot bath and stretched before winding them up.
- selected ether ethanol or diether is meant one which is soluble in 6% aqueous 'sodium hydroxide to the extent of at least 1% and no more soluble than 0.5% in the coagulating bath.
- el swelling are determined in both yarns spun and The numerical values of gel swelling given below for various yarn samples are usually determined according to the following procedure.
- the gel yarn is collected from the first feed wheel without stretch and prior to the hot dip bath by allowing the yarn to drop onto a square of cheese cloth for 3 minutes.
- the sample is centrifuged (3600 r.p.m.)
- the sample is washed free of acid, dried in an oven at 105 C. and weighed. The ratio of the gel weight to cellulose hydroxide.
- a sample of'each coagulated film is cut from the center, centrifuged and weighed. The weighed samples are then washed free of acid and salt, dried overnight at 105 C and reweighed.
- Gel 'swellings (grams of gel film per gram of cellulose) are determined for both modified and unmodifiedfilms. The ratio of the :gel swelling of the test item to the gel swelling of the unmodified viscose film is calculated. This numerical value is called the gel swelling ratio (films).
- the caustic content refers to the total alkalinity expressed as sodium It includes the free sodium hydroxide and that combined in the form 'of sodium carbonate, "sodium .trithiocarbonate, and sodium cellulose xanthate.
- EXAMPLE I A 5% cellulose and 6.5% total sodium hydroxide v'iscose modified 'with 0.5% phenoxyethanol (based on total weight of viscose) is prepared ih "the following manner. Alkali cellulose aged to the desired viscose viscosity (40 to 60 poises) is xanthated for 2 hours using 43% carbon disulfide'(based on air dry cellulose). The xanthate crumbs are dissolved in a solution of caustic, to which mixture the phenoxyethanol is added After mixing for a total time of 3 hours at 17 C. the freshly prepared viscose is filtered, deaerated and kept at 4 C.
- a yarn of 1100 denier-720 filaments (0.0025" spinneret hole diameter) is spun into a primary coagulating regenerating bath, consisting of 6.5% H 17.8% Na SO and 9.5% znso...
- the apparatus and general procedure used to spin the yarn described above are essentially the same as those used commercially in the so-called bobbin or spool spinning process.
- the specific conditions include a primary bath travel of 41 inches, a
- one or more other modifiers may be mixed into the viscose therewith.
- polyethylene glycols preferably with a molecular weight of from 300 Table II YARN AND CORD PROPERTIES FROM VISCOSE MODIFIED WITH VARIOUS ETHER ETHANOLS [5% cellulose, 6.5% NaOH, 43% CS2 viscose; 8.5% F2804, 17.5% M11804, 9.5% ZnSO; bath] Yarn Properties Cord Properties,
- ether modifiers of this invention may be combined with the ether modifiers of this invention to produce yarns and cords with substantial increases in physical properties and a lowering of gel swelling.
- An example of an ether ethanol in combination with polyethylene glycol and cyclohexylamine follows.
- Film gel swelling, bath solubility and 6%"aqueous NaOH solubilitytests are made on these as' 'well as on the compounds mentioned above. Althoiighyarn gl s'welli rigs and film Y gel swellings do not always -cor"relate, generally the modified potentiality or acornpound maybe 'judged from this test.
- the film gel swellin'gratio ratio of modified gel swelling to unmodified gel swelling
- glycol diethyl ether tetraethylene glycol diethyl ether
- ethylene glycol dimethyl ether is added.
- the freshly- 7 kept at .C. until spun, i.e., it is spun in the unripened state andhas' a'high salt index value, high xanthate sulfur content, and fairly low sodium trithiocarbonate content.
- The' viscose isspuninto 275 denier-100 filament yarn by demonstrating the improvement brought about by the viscose modifier.
- skin thickness of the yarn is greatly increased by the modifier.
- the zinc-free bath contains 11% sulfuric acid and 27% sodium sulfate while the zinc bath contains 8% sulfuric acid, 14% sodium sulfate, and 13% zinc sulfate.
- the yarn is given a bath travel of 30 inches using a roller guide.
- the apparatus and general procedure used to lead viscose into the bath and to collect the formed threads are essentially the same as those used commercially in the socalled bobbin or spool process.
- EXAMPLE XIV A viscose containing 1% diethylene glycol dimethyl ether is prepared and spun in the manner described in Example I. In this case, however, the viscose is allowed to ripen slightly and in the case of the zinc bath a higher acidity is used. The properties of these yarns along with those from unmodified control viscose are described in the table below. Yarns from viscose containing this modifier showed improvements similar to those obtained with tetraethylene glycol dimethyl ether.
- the yarn includes a bath temperature of C. and filaments are carried through a secondary bath of 1% sulfuric acid at 95-400 C.
- the yarn is wound on a bobbin at 28 yards per minute with the stretch obtainable at of the break tension.
- the resulting regenerated yarn is washed free of acid and salt and then dried. After twisting, the yarns are tested at 21 C. and 60% relative humidity.
- Viscoses containing 6.25% recoverablecellulose and 5.75% alkali are prepared from woodpulp sheets in the conventional manner using 38% carbon disulfide, based on the weight of the air dry pulp, in the xarithation step.
- the viscoses are filtered, deaerated and ripened to asalt index value of 16 to 17 and a viscosity of about 30 poises.
- Phenoxyethanol in the amounts indicated below, is addedto-the'viscoses used for the preparation of yarns A, B and C. No modifier-is added to the viscose used for preparing yarn D.
- the viscoses are extruded at a temperature of about 44 C. into a spinning bath maintained at a temperature stretch imposed on the yarn up to the feed wheel is about
- the yarn is-stretched an additional 20% by passing it to a second feed wheel having a larger diameter than the first feed wheel but rotating at the same speed 'asthe first.
- the ether ethanols and diethers of this invention should be'used in the viscose at concentrations of at least 0.06% and ingeneral, it is unnecessary Preferably, these compounds will beused in viscose at concentrations of from 0.1% to 1;0% based on the total weight of-viscose.
- Theviscose used inthe process of the invention may "be a variety of types; for example, it may be from wood ip'ulpycotton linters, mixtures of the 'two, or even other types'of cellulose.
- the composition of the viscose may alsobe varied widely. Forexample, it may have a cellulose content of from 4% to 10% or even more and an alkali content of. from 4% to 9% or more.
- the standard viscoses of the'indus'try i.e., those having between 5% and 7% cellulose-and between 4% and 7% alkali are fpreferably used.
- the amount of carbon bisulfide used in xanthation can be 25% to 60% or higher (based on It has been found of this invention-are added and there appears to be an "advantage in stretchabilityand level of the yarn properties if salt indices higher than 5 are used. It is generally necessary to use 30% or more of carbon bisulfide to obgel swelling an'dyarn and cord properties are also obtained with normally ripened viscose.
- composition of the spinning bath is not critical when the modifiers of this invention are present-in the viscose.
- An improvement in yarn and 'cord properties and reduction of gel swelling are obtained with acid salt baths free of zinc salt or salts of other heavy metals.
- acid salt baths free of zinc salt or salts of other heavy metals.
- Useful baths include coagulating regenerating baths containing from about 4% to about 12% sulfuric acid, about 5% to about 25 sodium sulfate'and about 1% to about 15% zinc sulfate.
- the bath temperature range should be from 40 to 75 C.
- the bath temperature as well as the bath composition and-especially bath acid may need to be adjusted depending on the specific modifier or combination of modifiers used and the concentration of these modifiers in the viscose.
- Optimum results can only be secured by carefully balancing the spinning bath composition with the specific modified viscose at hand together with bath travel, bath temperature and spinning 200 inches or more in the primary bath by means of a multiple roller setup which gradually applies tension to the traveling filaments and thereby orients them while they are still plastic.
- the preferred method is to apply a part or all the stretch beyond the primary bath in a secondary bath or after the yarn is acted upon by the secondary bath.
- the secondary bath may consist simply of water or dilute (1% to 3% sulfuric acid) or it may have the same composition as the coagulating bath but at a greater dilution, e.g. one fourth of the concentration of the coagulating bath.
- the yarn may be given a travel of 10 to 50 inches more or less in the secondary bath of hot water or hot dilute bath.
- the temperature of the secondary bath is preferably between 50 C. and 100 C. Stretches of to are preferred for producing high tenacity yarn and 20% to 30% for textile type yarns. The amount of stretch ap plied depends on the properties desired for the yarn. While the bobbin process is used in the examples, it is used in the examples, it
- the yarn is immaterial whether spinning is by bobbin, bucket or continuous processes.
- the yarn is washed free of acid and salt after which it may be dried in the form of its spin package or may be withdrawn wet and dried on the run. It may be twister-dried or slasher-dried with suitable controls to hold dry elongation at the desired level.
- Spinning may be carried out with the aid of spinning tubes such as described in Millhiser U.S. Patent 2,440,- 057 or in Drisch et al. U.S. Patent 2,511,699.
- These tubes of relatively small diameter and of substantial length confine the bath filaments in their critical stage of formation so that no substantial tension is imposed on the filaments because the speed of the concurrent bath flow through the tube is maintained only slightly below the speed of the filament bundle passing through the tube. It is thus possible to materially increase the rate of spinning over methods earlier described without substantial sacrifice in the desirable properties set forth above.
- novel and improved yarnsobtainable through the process of this invention can in general be used instead of regular regenerated cellulose yarns for any purpose where the latter are finding applications, more particularly in the textile and tire cord industries.
- cross sections of the yarns of this invention also exhibit a preponderance of skin over core, in many cases being substantially 100% skin, and these yarns exhibit greater toughness as measured by greater fatigue resistance and longer life in reinforced rubber products.
- the combination of high tenacity yarns and a high ratio of conversion of yarn strength to cord strength represents a material advance in the art.
- a process for producing a regenerated cellulose structure having improved fatigue resistance which comprises adding to the viscose at least 0.06% by weight, based on the weight of the resultant viscose, of an ether having the formula:
- R is a member of the group consisting of alkyl and aryl
- n is an integer of from 1-4
- R is a member of the group consisting of hydrogen, alkyl and aryl
- the said ether being soluble in 6% aqueous sodium hydroxide to the extent of at least 1% by weight and soluble only to about 0.5% by weight in said coagulating bath.
- sai coagulating bath contains up to about 15% by weight zinc sulfate.
- a process in accordance with claim 1 wherein the temperature of the coagulating bath is from about 40 C. to about C.
- a process for the preparation of a regenerated cellulose structure having improved fatigue resistance which comprises adding to viscose about 0.1% to about 1.0% by weight based on the weight of the resultant viscose, of an ether having the formula:
- R is a member of the group consisting of alkyl and aryl
- n is an integer of from 1 to 4
- R is a member of the group consisting of hydrogen, alkyl and aryl
- said ether acting to reduce the gel swelling of the structure, extruding the resultant viscose, in the substantial absence of leuco vat coloring matter, into a coagulating and regenerating bath containing from about 4% to about 12% by weight sulfuric acid, about 5% to about 25% by weight sodium sulfate and about 1% to about 15 by weight zinc sulfate and immediately thereafter stretching the resulting structure having the reduced gel swelling; the said bath being at a temperature of about 40 C. to about 75 C. and the said ether being soluble in 6% aqueous sodium hydroxide to the extent of at least 1% by weight and soluble only to about 0.5 b weight in the said coagulating bath.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Description
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US584450A US2962341A (en) | 1956-05-14 | 1956-05-14 | Viscose modification |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US584450A US2962341A (en) | 1956-05-14 | 1956-05-14 | Viscose modification |
Publications (1)
Publication Number | Publication Date |
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US2962341A true US2962341A (en) | 1960-11-29 |
Family
ID=24337363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US584450A Expired - Lifetime US2962341A (en) | 1956-05-14 | 1956-05-14 | Viscose modification |
Country Status (1)
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US (1) | US2962341A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3033696A (en) * | 1955-03-18 | 1962-05-08 | American Enka Corp | Manufacture of rayon |
US3047412A (en) * | 1961-04-13 | 1962-07-31 | Gen Aniline & Film Corp | Viscose composition and method of spinning |
US3151194A (en) * | 1961-09-01 | 1964-09-29 | American Enka Corp | Process for the manufacture of shaped bodies from viscose, and the products thus obtained |
EP2706133A1 (en) * | 2012-09-07 | 2014-03-12 | Kelheim Fibres GmbH | Method for manufacturing viscose fibres |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2040712A (en) * | 1934-02-08 | 1936-05-12 | Courtaulds Ltd | Manufacture and production of colored artificial filaments, threads, bands, and the like |
US2065668A (en) * | 1932-01-29 | 1936-12-29 | Dreyfus Henry | Manufacture and treatment of filaments and the like |
GB541099A (en) * | 1940-05-11 | 1941-11-12 | Courtaulds Ltd | Improvements in and relating to the manufacture and production of artificial threads and the like articles from viscose |
US2393817A (en) * | 1942-10-19 | 1946-01-29 | Rayonier Inc | Production of cellulosic products |
US2535044A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
US2860480A (en) * | 1956-04-18 | 1958-11-18 | Du Pont | Regenerated cellulose structures and process for producing them |
-
1956
- 1956-05-14 US US584450A patent/US2962341A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2065668A (en) * | 1932-01-29 | 1936-12-29 | Dreyfus Henry | Manufacture and treatment of filaments and the like |
US2040712A (en) * | 1934-02-08 | 1936-05-12 | Courtaulds Ltd | Manufacture and production of colored artificial filaments, threads, bands, and the like |
GB541099A (en) * | 1940-05-11 | 1941-11-12 | Courtaulds Ltd | Improvements in and relating to the manufacture and production of artificial threads and the like articles from viscose |
US2393817A (en) * | 1942-10-19 | 1946-01-29 | Rayonier Inc | Production of cellulosic products |
US2535044A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
US2860480A (en) * | 1956-04-18 | 1958-11-18 | Du Pont | Regenerated cellulose structures and process for producing them |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3033696A (en) * | 1955-03-18 | 1962-05-08 | American Enka Corp | Manufacture of rayon |
US3047412A (en) * | 1961-04-13 | 1962-07-31 | Gen Aniline & Film Corp | Viscose composition and method of spinning |
US3151194A (en) * | 1961-09-01 | 1964-09-29 | American Enka Corp | Process for the manufacture of shaped bodies from viscose, and the products thus obtained |
EP2706133A1 (en) * | 2012-09-07 | 2014-03-12 | Kelheim Fibres GmbH | Method for manufacturing viscose fibres |
WO2014037191A1 (en) * | 2012-09-07 | 2014-03-13 | Kelheim Fibres Gmbh | Process for producing viscose fibers |
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