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
  • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
• • 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
  • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
  • D01D10/04—Supporting filaments or the like during their treatment
  • D01D10/0436—Supporting filaments or the like during their treatment while in continuous movement
  • D01D10/0472—Supporting filaments or the like during their treatment while in continuous movement the filaments being supported on endless bands
• • 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
  • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
  • D01D10/04—Supporting filaments or the like during their treatment
  • D01D10/0436—Supporting filaments or the like during their treatment while in continuous movement
  • D01D10/0481—Supporting filaments or the like during their treatment while in continuous movement the filaments passing through a tube
• • 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties

Definitions

• This invention relates to the production of artificial filaments, threads, fibres, bands and the like, hereinafter referred to generally as threads, from casein of animal or vegetable origin, for example lactic or milk casein, peanut protein, soya bean protein, castor bean protein and similar fibre-forming proteins.
• casein of animal or vegetable origin for example lactic or milk casein, peanut protein, soya bean protein, castor bean protein and similar fibre-forming proteins.
• German patent specification No. 748,450 describes a process of dyeing and printing natural or artificial protein fibres or mixtures of such fibres, wherein the fibres, either during or after the dyeing, are treated with methanol in the presence of an esterification catalyst.
• the object of the present invention is to improve the wet properties of protein threads.
• protein threads having improved wet properties are produced by hardening freshly extruded protein threads in a bath containing formaldehyde and one or more metal salts until the threads are resistant to cold water, treating the hardened threads in a bath comprising methyl alcohol or ethyl alcohol together with an esterification catalyst such as sulphuric acid to eiiect esterification of the threads and then subjecting the esterified threads to a curing treatment, that is to say, either a hardening treatment in a bath CQnr. taining formaldehyde and one or more metal salts or an insolubilising treatment.
• an esterification catalyst such as sulphuric acid
• the esterification of the hardened threads is preferably effected at a raised temperature, for example at 35 to 50 centigrade.
• the preferred esterification catalyst is sulphuric acid but other catalysts such as methyl sulphuric acid and ethyl sulphuric acid may be use.
• Preferred hardening baths for use in the pres ent invention are those containing formaldehyde and sodium sulphate although other salts such as magnesium sulphate or aluminium sulphate may also be present in addition to or instead of the sodium sulphate.
• the hardening bath may also contain an acid such as sulphuric acid.
• insolubilising agents for treating the esterified threads are acetic anhydride as described in Brit ish patent specification No. 495,385 and compounds giving rise to cyanate ions as described in British patent specification No. 614,506.
• the aluminium sulphate baths described in the specification of British application No. 1810'2/50, which effect hardening and insolubilising simultaneously, may also be used.
• the treatment of the esterified threads with cyanates can conveniently be effected by applying to the thread an aqueous composition containing a soft-finishing compound together with a cyanate and, after removing surplus liquor, baking the thread for a short time, for example at to 10 centigrade.
• the prehardened fibres either alone or in admixture With other fibres may be knitted, woven or otherwise formed into a fabric and the fabric may then be treated in an esterification bath followed by a second hardening or insolubilising bath in accordance with the invention.
• the esterification liquid containing sulphuric acid and methyl alcohol or ethyl alcohol may also contain Water preferably in a proportion not exceeding 30 per cent by weight based on the weight of the alcohol. Proportions of water of the order of 20 to 25 per cent are particularly suitable.
• the use of esterification media containing water is usually more economic as compared with the use of similar media which are substantially free from water.
• Baths containing '75 to per cent of methyl alcohol or ethyl alcohol and 25 to 20 per cent of water, with to 240 grams per litre of sulphuric acid may be used with good results.
• Such esterification is preferably effected at raised temperatures, temperatures of from 35 to 50 centigrade being particularly suitable. Treatment times are not critical and may conveniently vary from /2 hour to 3 hours, depending on the temperature used and the concentration of the esterification bath.
• dialkyl sulphate for example in a proportion of about 30 per cent by weight based on the weight of the alcohol, assists in the esterification.
• the preferred dialkyl sulphate is diethyl sulphate.
• the process according to the invention produces protein threads which are generally white in colour and have reduced water imbibition. Imbibition is defined in Cameron and Morton, Permanent Finishes on Viscose Rayon, Journal of the Society of Dyers and Colorists, October 1948, page 331, and in Proceedings, Journal of the Textile Institute 40, page P678 (1949), as the percent by weight of water retained on the oven dried fiber after centrifuging a 0.5 gram sample for minutes at 1000 g.
• the fastness to washing of threads dyed with a dispersed dye such as Azo-Geranine (Colour Index No. 31) and with crome dyes is also improved.
• the threads are also stable to normal hot acid dyebaths containing acid dyes, chrome-complex acid dyes, chrome dyes, and also to normal dyebaths containing direct dyes and solubilised sulphur dyes.
• the process according to the invention may include a cutting operation at any convenient stage; the staple fibres produced are particularly suitable for blending with wool in the manufacture of milled articles such as blankets, since the protein fibres are not adversely affected to any appreciable extent by the milling process.
• Example 1 A percent solution of milk casein in 1 percent aqueous caustic soda solution was extruded into a coagulant bath.
• the resultant threads after hardening in formaldehyde were stretched 400 percent and were then hardened further by immersion for 2 hours in a bath at 50 centigrade containing, in each litre of solution, 10 grams of formaldehyde and 400 grams of sodium sulphate; the pH value of the bath was 3.5.
• the threads were then pressed free from surplus liquor, washed in water, again pressed and then immersed for 4 hours in a bath at 45 centigrade consisting of a mixture of 7 parts of concentrated sulphuric acid (specific gravity 1.84) and 33 parts of ethyl alcohol.
• the esterified fibres were then washed in water and hardened again for 2 hours in a bath at 45 centigrade containing, in each litre, 10 grams of formaldehyde and 400 grams of sodium sulphate. The fibres were finally washed in water and dried.
• the imbibition of the threads obtained in a 1 percent aqueous sodium carbonate solution was 44 percent as compared with 125 percent for corresponding threads which had been hardened only.
• Example 2 A 20 percent solution of milk casein in 1 percent aqueous caustic soda solution was extruded into a coagulant bath.
• the resultant threads after hardening in formaldehyde were stretched 400 percent and were then hardened further by immersion for 2 hours in a bath at 50 centigrade containing in each litre of solution, 10 grams of formaldehyde and 400 grams of sodium sulphate; the pH value of the bath was 3.5.
• the threads were then pressed free from surplus liquor, washed in water and then cut to 2 inch staple lengths.
• the cut staple was dried in a current of warn air. blended with 3 times its weight of wool noils and the blend was spun using the woollen system into yarn of 12 counts.
• the yarn was then woven into a cloth suitable, after milling, for coatings.
• a sample of the fabric was then soaked for 8 hours at 35 centigrade in 20 times its weight of a mixture of 1 part of sulphuric acid and 4 parts of methylated spirit.
• the fabric was then washed in water till free from acid, and hardened for 2 hours in a bath at 45 centigrade containing, in each litre, 10 grams of formaldehyde and 400 grams of sodium sulphate.
• the fabric was washed in water, dried and then subjected to a milling operation in a Williams Peace milling machine, using 2Tw. sodium carbonate solution containing percent of soap, at 50 centigrade. Under these conditions the fabric was found to be dimensionally stable, both as regards expansion on wetting and the development of undue shrinkage during milling; the fabric resisted the mechanical action of the milling machine and no holes or other faults developed during the operation.
• Example 3 A 20 percent solution of peanut protein in 1 percent aqueous caustic soda solution was extruded into a coagulant bath.
• the resultant threads after hardening in formaldehyde were stretched 500 percent and were then hardened further by immersion for 2 hours in a bath at 35 centigrade containing, in each litre of solution, 10 grams of formaldehyde, 300 grams of sodium sulphate and 360 grams of sulphuric acid.
• the threads were then pressed free from surplus liquor, washed in water, again pressed and then immersed for 2 hours in a bath at 45 centigrade consisting of a mixture of- 1 part of sulphuric acid and 4 parts of methylated spirit (74 o. p.).
• the esterified fibres were then washed in water and hardened for 2 hours in a bath, at 40 centigrade, containing in each litre, 10 grams of formaldehyde and 400 grams of sodium sulphate. The fibres were then washed and dried.
• the imbibition of the threads obtained in a 1 percent aqueous sodium carbonate solution was 40 per cent as compared with 81 per cent for corresponding fibres which had been hardened and insolubilised only.
• Example 4 A sample of casein thread hardened as described in Example 1 was immersed for 1 hour in a bath at 50 centigrade consisting of a mixture of 4 parts of ethyl alcohol and 1 part of water and containing grams of sulphuric acid per Example 5 The procedure described in Example 4 was repeated using methyl alcohol in place of ethyl alcohol. The imbibition in a 1 percent aqueous sodium carbonate solution of the thread obtained was 58.4 percent.
• Example 6 Casein threads hardened as described in Example 1 were soaked in methyl alcohol at 35 centigrade. Surplus alcohol was squeezed out and the fibres were then esterified for one hour at a temperature of 35 centigrate with parts by weight of a liquor consisting of 6.2 parts by volume of methyl alcohol, 2.5 parts by volume of diethyl sulphate and 1 part by volume of sulphuric acid. The esterified fibres were washed until they reacted neutral to methyl red, hydro-extracted and rehardened, washed and dried as described in Example 1.
• Example 7 Casein fibres extruded and stretched as described in Example 1 were hardened for 2 hours at a temperature of 50 centigrade in a liquor containing, in each litre, 250 grams of aluminium sulphate, 250 grams of sodium sulphate and 10 grams of formaldehyde. The fibres after removal of same composition as described in Example 6 for one hour at centigrade. The esterified fibres were washed and rehardened for 2 hours at centigrade using the same liquor as for the initial hardening. The fibres were finally washed and dried.
• the imbibition of the product was 45 percent.
• Example 8 fhe moist fibres obtained as described in Example 7 up to the re-hardening stage were imusing as a control a thread prepared as described in Example 8 but excluding only the esterification step.
• the thread prepared as described in the example was substantially unaffected by the dyeing treatment whereas the dyed control threads were hard and rather brittle.
• Example 9 Casein fibres which had been initially hardened as described in Example 7 were soaked in methyl alcohol at a temperature of 40 centigrade and the excess alcohol removed by squeezing.
• the fibres were esterified with a liquor consisting of methyl alcohol containing in each litre grams of sulphuric acid.
• the esterified fibres were washed free from acid and hydro-extracted.
• the moist fibres were impregnated with a 2 percent solution of sodium cyanate containing 0.1 percent of a soft finish and the excess liquor squeezed out.
• the fibres Were heated at 70 centigrade for 10 minutes, washed in water and finally dried.
• the imbibition oi the product was 70 percent.
• Example 10 fhneads, extruded, hardened and stretched as described in Example 1, were hardened further for 3 hours in a bath at 45 centigrade containing in each litre 550 grams of aluminium sulphate and 20 grams of formaldehyde.
• the threads were washed free from excess liquor and were then esterified by immersion for 45 minutes in methyl alcohol containing 350 grams per litre of sulphuric acid, this liquor being at a temperature of 35 centigrade.
• the threads were Washed until they were free from acid and then immersed for 20 minutes in a 4 percent aqueous sodium cyanate solution. Excess solution was removed from the threads by squeezing and the threads were dried at 65 centigrade.
• a bath comprising an alcohol chosen from the group consisting of methyl alcohol and ethyl alcohol, together with an esterification catalyst and water, said water being in a proportion not exceeding 30% by weight based on the weight of the alcohol, and then rehardening the esterified thread by immersing said esterified thread in a bath containing formaldehyde and a metal salt chosen from the group consisting of sodium sulphate, magnesium sulphate, aluminum sulphate and mixtures of said salts, until the imbibition of the threads in a 1% aqueous sodium carbonate solution is between about 40 and about 64.9% based on the weight of the oven-dried thread.

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  • NL NL65080D patent/NL65080C/xx active
  • BE BE507677D patent/BE507677A/xx unknown
  • BE BE526592D patent/BE526592A/xx unknown
  • NL NL76966D patent/NL76966C/xx active
  • BE BE502874D patent/BE502874A/xx unknown
  • NL NL83770D patent/NL83770C/xx active
  • NL NL79753D patent/NL79753C/xx active
  • BE BE474353D patent/BE474353A/xx unknown
  • DE DENDAT906847D patent/DE906847C/de not_active Expired
• 1946
  • 1946-07-17 GB GB21376/46A patent/GB614506A/en not_active Expired
• 1947
  • 1947-07-01 FR FR948704D patent/FR948704A/fr not_active Expired
• 1948
  • 1948-12-31 DE DEP28708D patent/DE842827C/de not_active Expired
• 1951
  • 1951-04-12 US US220727A patent/US2691568A/en not_active Expired - Lifetime
  • 1951-04-29 DE DEC4130A patent/DE898658C/de not_active Expired
  • 1951-05-02 FR FR1045696D patent/FR1045696A/fr not_active Expired
  • 1951-11-13 US US255912A patent/US2684282A/en not_active Expired - Lifetime
  • 1951-12-10 FR FR62218D patent/FR62218E/fr not_active Expired
  • 1951-12-12 DE DEC5907A patent/DE905306C/de not_active Expired
• 1952
  • 1952-06-13 GB GB14910/52A patent/GB722934A/en not_active Expired
• 1953
  • 1953-03-05 GB GB6115/53A patent/GB741740A/en not_active Expired
• 1954
  • 1954-03-04 FR FR65531D patent/FR65531E/fr not_active Expired
• 1955
  • 1955-03-02 GB GB6131/55A patent/GB778258A/en not_active Expired

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