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 a process for the manufacture of fibers, threads, foils, films and other shaped objects by spinning viscose in acid spinbaths, and preferably spinbaths containing sulphuric acid, in such manner as to confer upon the resulting products certain improved properties as hereinafter described.
• the invention also relates to the resulting improved products.
• One of the principal objects of thepresent invention is to provide a new and improved method for spinning artificial products such as threads and other shaped objects from viscose in such manner as to confer upon them greatly improved properties as regards their strength and elasticity.
• a further object of the invention is to provide a new and improved method for producing products of the'kind just indicated having unusually strong and well' defined peripheral zones, i.e., the so-called skin structure or efiect mentioned above.
• a still further object of the States Patent invention is to provide improved products of the kind" indicated.
• the process according to the present invention is characterized in that there is employed a viscose which concertain organic substances which are soluble, in
• viscose and which form with the Zinc in the spinning product temporarily stable zinc chelates said viscose being spun in a zinc-containing spinbath and the freshly spun products being subjected to stretching.
• the substance which combines with the metal contains two or more donor groups so that one or more rings are formed, the resulting structure is said to be a chelate compound, or metal chelate, and the donor is said to be a chelatingagent.
• chelating agents are mole-. cules which contain at the same time two or more atom groups each having available a main valency or a subvalency by which said atom groups may retain between them a metal ion, in the present case therefore a zinc ion, in the manner as indicated by the Greek word chelae (in the manner of a claw or a pair of tongs) with binding forces at two or more sides. These binding forces emanate especially from atoms such as N, S and sometimes also 0. It is also possible to consider the chelates involved in the process according to the present invention as a kind of interior (or internal) metal complex salt.”
• the viscose employed for spinning contains certain organic chelate forming substances or classes of substances, i.e., substances which at the instant of formation of the product, eg a fiber or a thread or a foil, form with Zinc temporarily a Zinc chelate.
• organic chelate forming substances or classes of substances i.e., substances which at the instant of formation of the product, eg a fiber or a thread or a foil, form with Zinc temporarily a Zinc chelate.
• Not all existing or known chelate formers are suitable for use in the process according to the present invention, however, since they have to comply with certain requirements set forth hereinafter. Consequently, only those substances or classes of substances listed hereinafter are contemplated as falling Within the scope of the present invention.
• the chelate formers must be at least slightly soluble in the viscose, since it has been found that the chelate formers can only give the desired elfect in solubilized condition.
• the zinc chelate formed by the chelate former and the zinc must have a certain restricted or limited stability. This stability must be such that the zinc chelate is stable at a higher pH so that the chelate formers can perform their specific chelate function under the circumstances mentioned. On the other hand, they must become unstable as the pH lowers during the formation of the product so that they may at the right moment release or give up the zinc ion so as to perform its fume tion as link former between the cellulose xanthate molecules.
• Stretching to a relatively great extent may be done in a so-callcd one-bath process as well as in a two-bath process.
• Organic compounds having the thiazole nucleus e.g., thiazole derivatives such as mercaptobenzothiazole.
• Organic compounds having the irnidazole nucleus e.g., imidazole derivatives such as mercapto-benzimidazole.
• Organic xanthic acids and their alkali metal salts especially the sodium salts, e.g., sodium-n-amyl-xanthate.
• Organic compounds having an OH-radical participating in chelate formation said OH-radical having an acidic character, and preferably occupying a position in the molecule relatively close to a second radical having an active main valency or subvalency capable of coacting with said OH-radical in chelate formation; e.g., 8oxyquinoline.
• alcoholic OH-radicals are not active; phenolic OH-radicals (dissociation constant 10' are in contrast thereto very active when used according to the invention. Due to the higher dissociation constant a phenolic OH-radical has in the alkaline medium of the viscose much stronger electron donor properties than an alcoholic OH-radical.
• the amount of the foregoing chelate-forming substances to be employed in the viscose may be very small, relatively speaking. In some cases about 0.05% and less, based on the weight of the viscose, was found to be suflicient to obtain the desired effect. It is, however, also possible to employ larger proportions of the chelateforming substances, say up to 1% or more by weight of the viscose.
• the zinc content of the spinning bath is at least 2-3% by weight of zinc sulphate, since at lower concentrations of the zinc sulphate the physical properties of the products are generally somewhat less satisfactory.
• spun viscose products with especially good properties are obtained when the sulphuric acid content of the spinning bath, expressed in percent by weight, is at least about 0.8 times the alkali content of the viscose, also expressed in percent by weight; however, the value 1.3 times the alkali content of the viscose should not be notably exceeded for the sulphuric acid content of the spinbath.
• the skin structure which the spun products obtained according to the process of the present invention show in cross section, and which is to a great extent uniformthroughout the total cross section, is always accompanied by especially favorable physical properties such as high break strength, high double-loop strength and also high abrasion resistance, whereas the swelling power in water is small.
• the wet strength is high relative to the dry strength.
• Example I A viscose with a cellulose content of 8.4% and an alkali content of 4.8% was prepared by xanthating with 33% CS based on the cellulose. 0.15% Z-mercaptobenzothiazole, based on the viscose, was incorporated therein.
• the thus-treated viscose was spun with a xanthate ratio of 0.50, a viscosity of 35 sec. (falling-ball test), and a ripeness of 12 Hottenroth.
• the spinning bath had the following composition: 4% H 50 18% Na SO 4% ZnSO and the remainder water.
• the temperature of the spinning bath was 50" C. and the im-' mersion stretch amounted to 40 cm. After a stretch of 75% the final draw-off speed amounted to 35 m./min.
• the finished thread contained 200 filaments and had a total titre of 400 denier.
• a thread was obtained with a good skin structure and a swelling capacity of only 75%.
• the product was characterized by a good abrasion resistance while the bending strength and the double-loop strength were also very good.
• the mechanical properties were as follows: dry strength 270 g./100 denier, dry elongation 20%, wet strength 142 g./100 denier, wet elongation 35%.
• Example 11 In the preparation of a viscose with a 7.3% cellulose content and a 6.8% alkali content, 8-oxyquinoline in the amount of 0.1%, calculated on the viscose, was added to the alkali cellulose after which the alkali cellulose was xanthated with 36% CS The resulting viscose was spun with a xanthate ratio of 0.48, a ripeness of 22 Hottenroth, and a viscosity of 60 sec. (falling-ball test) according to the two-bath spinning method. The first bath had a temperature of 70 C. and an immersion stretch of 120 cm. was used. The composition of the first bath was 8% H 19% Na SO 6% ZnSO and the remainder water.. The second bath had a temperature of C. and consisted of spin bath diluted to a H 80 concentration of 1.5%. The stretch was 110% and the final draw-off speed 70 m./min.
• a thread was spun of 1150 denier with 660 filaments and having excellent physical properties.
• the swelling in water was 70% and both the double-loop strength and abrasion resistance were very good.
• the dry strength amounted to 401 g./ denier, the dry elongation 23.4%, the wet strength 310 g./100 denier, and the wet elongation 28%.
• the fatigue resistance of a tire cord manufactured from this thread was very good.
• the viscose contained 0.2% Na-n-amylxanthate.
• Thethread thereby obtained had a swelling capacity of 80% with a good skin structure.
• the dry strength amounted to 290 g./100 denier, the dry elongation 21%, the wet strength 148 g./100 denier, and the wet elonga- Q J 43%..
• Example IV A viscose having a cellulose content of 7.7% and an alkali content of 5.5%, and which contained 0.1% of S-mercapto-3 -phenyl-2-thio-1,3,4thiodiazolon-2- (calculated on the viscose), was spun at a xanthate ratio of g 0.52,- a viscosity of 57 sec. (falling-ball test), and a Hottenroth ripeness of 19.5 according to the two-bath process while being stretched by 90%. The final col- ,lectingspeed amounted to 60 m./min. A thread of 1840 denier and having 1000 filaments was obtained.
• the first bath contained 6% of H 50 17.8% of Na SO and 3.8% of ZnSO
• the temperature of this bath amounted to. 60 C.
• the second bath contained 2% of H SO and had a temperature of 90.
• the threads obtained showed a good skin structure.
• the swelling in water amounted to 70%.
• the double-loop strength, the resistance to abrasion, and the fatigue resistance of a tire cord made from this yarn were very good.
• the dry strength was 4 g./denier at a dry stretch of 23%.
• surface active substances When surface active substances are employed, they may be added either to the viscose or to the spinning bath, or to both. They may be of the anion-active, cation active or non-ionic type.
• praestabit oil lauryl tniethyl ammoniumchloride and the polyethylene oxide derivative on the market under the name of Hills V 1011 T, which has the structure:
• the surface active substances may be added to the viscose in various proportions such as 0.2-0.6, 02-075 and 0.1-1% by weight, respectively, based on the cellulose in the viscose, and lauryl pyridiniumchloride, the latter being added to the spinbath in proportions of 20- 100 mg./kg. spinbath.
• Example V A viscose having a cellulose content of 7.7% and an alkali content of 5.5 to which 0.12% of S-mercapto- 3-p-bromophenyl-2-thio-l,3,4-thiodiazolon-2 and 0.3% of a surface active polyethylene oxide derivative marketed under the name of Hiils V 1011 T had been added, was spun at a xanthate ratio of 0.50, a viscosity of 60 sec. (falling-ball test), and a Hottenroth ripeness of 180' in a spinbath at 60 C. containing 6% of H SO 18.5% of Na SO and 3.8% of ZuSO In this bath a tube with two portions of different diameter was arranged at a distance of 2 cm.
• the diameter of the tube portion directly in front of the spinneret was 21.5 mm. and the diameter of the second tube portion was 26 mm.
• the lengths of the narrow and the wide tube portion were 40 and 14 cm., respectively.
• a cone-shaped tube portion 6 cm. in length constituted the connection between both tube portions.
• the threads thus spun were finally stretched in a second bath containing 2% of H 80, and having a temperature of C.
• the final collecting speed was 80 m./min.
• the dry strength amounted to 4 g./denier at a stretch of 25%. Spinning at the indicated speed was not possible without the use of a tube and a surface-active substance.
• Example VI A viscose with a cellulose content of 8.4% and an alkali content of 4.8% prepared by xanthating with 33% CS based on cellulose, contained 0.15% Z-mercapto-benzothiazole and 0.04% of a polyethylene oxide derivative available on the market under the name Hills V 1011 T (both substances calculated on the viscose).
• the thustreated viscose was spun with a xanthate ratio of 0.50, a viscosity of 35 sec. (falling-ball test), and a ripeness of 12 Hottenroth, and the spinning bath contained 4.0% H 80 18.0% Na SO 4.0% ZnSO and the remainder water.
• the temperature of the spinbath was 50 C. and the immersion stretch was 40 cm. After a stretching of 75% the final draw-oil speed amounted to 60 m./min., while in the absence of the polyethylene oxide derivative difficulties occur at draw-off speeds above 40 m./ min.
• the thread obtained consisted of 200 filaments with a total titre of 400 denier. It had a good skin structure and a swelling capacity of about 70%.
• the mechanical properties were as follows: dry strength 300 g./l00 denier, dry elongation 25%, wet strength 170 g./ denier, and wet elongation 35%.
• the improvement that comprises incorporating in the viscose about 0.051.0% by weight of the viscose of an organic substance selected from the group consisting of 5-mercapto-3-phenyl-2-thio- 1,3,4-thiodiazolon-2; 5-mercapto-3-p-bromophenyl-2-thio- 1,3,4-thiodiazolon-2; and 8-oxyquinoline which is soluble in viscose and which forms with zinc in the product as it is formed, an alkali stable zinc chelate, spinning said viscose in an aqueous sulphuric acid spinbath containing zinc sulphate, and stretching the freshly spun products thereby obtained.
• an organic substance selected from the group consisting of 5-mercapto-3-phenyl-2-thio- 1,3,4-thiodiazolon-2; 5-mercapto-3-p-bromophenyl-2-thio- 1,3,4-thiodiazolon-2; and 8-oxyquinoline which is soluble in viscose and which forms with zinc in the product

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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)

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Citations (12)

• 0
  • BE BE539699D patent/BE539699A/xx unknown
• 1955
  • 1955-08-15 CH CH339316D patent/CH339316A/de unknown
  • 1955-08-19 FR FR1135878D patent/FR1135878A/fr not_active Expired
  • 1955-10-17 US US541045A patent/US2958569A/en not_active Expired - Lifetime

Patent Citations (12)

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