US2426861A - Process for improving the properties of water-insoluble artificial protein fibres - Google Patents

Process for improving the properties of water-insoluble artificial protein fibres Download PDF

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US2426861A
US2426861A US303158A US30315839A US2426861A US 2426861 A US2426861 A US 2426861A US 303158 A US303158 A US 303158A US 30315839 A US30315839 A US 30315839A US 2426861 A US2426861 A US 2426861A
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water
casein
fiber
solution
insoluble
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US303158A
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Comolli Giampiero
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Sandoz AG
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Sandoz AG
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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/046Material containing basic nitrogen containing amide groups using metallisable or mordant dyes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005Casein
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F4/00Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/24Halides of elements of Groups 6 or 16 of the Periodic Table, e.g. chromyl chloride
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates

Definitions

  • the artificial fibre when subjected to the treatment hereinafter described, undergoes an action similar to the action produced on depilated skins when subjected to chrome tanning with one or two immersions, which acquire great tenacity and powerful resistance to stretching and are not affected by boiling water.
  • the treatment which is covered by this invention and can be used in the actual manufacture of artificial fibres formed of or containing protein-like substances, is based on the use of salts of chromium (chrome alum, chromium sulphate,
  • the treatment may be effected with two baths, the first containing for example sodium or potassium bichromate and the other containing products capable of converting the compounds of chromic anhydride into compounds of chromium sesquioxide.
  • Example 1 Artificial fibre prepared from casein is impregnated in a bath containing grams per litre of potassium bichromate with the addition, if desired, of a mineral acid. After the impregnation of the fibre it is squeezed and placed in another bath containing 100 grams per litre of sodium bisulphite and then thoroughly washed with water. The fibre so treated acquires all the properties above mentioned (better resistance to stretching, wear, boiling water, etc.).
  • Example 2 Artificial fibre treated as in Example 1 is dyed with chrome dyes by the afterchroming process as well as in the dyeing process with a single bath.
  • the alkaline iulling of the dyed material does not exercise any negative influence upon the shade and the resistance of the fibres, whilst similar dyeings executed on untreated fibre are practically unusable after having been subjected to alkaline fulling.
  • Example 100 parts or casin staple fibres are treated in a milling drum during minutes with a 30-40" C. warm solution of 8.10.D ,s of sodiumor potassium bichromate in 400-500 parts of water.
  • the textile materlaltreated and dyed according to the example possesses a much better touch and better dynamometric properties as compared with the material that has not been subjected to the tanning operation.
  • Example 7 100 parts of casein yam are treated during 18 hours at ?"C. in a solution of the following composition:
  • the casein fibre which is colored in a clear olive green shade possesses a smooth touch which remains, even after a subsequent dyeing in a bath containing mineral acid.
  • the resistance to breaking and the elasticity of the casein fibre treated in this manner is much better as compared with the casein fibre which has not been subjected to the above treatment.
  • a process for producin water-insoluble artificial casein fiber which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinnin and hardening process, with a solution of a water-soluble chromium'compound, and then converting the latter,
  • a process for producing water-insoluble artificial casein fiber which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinning and hardening process, with a solution of a water-soluble salt of chromic acid, and then converting the latter into a water-insolubble chromium compound by treatment of the impregnated fiber with a reducing agent, thereby causing the formation and fixation of the water-insoluble chromium compound in and on the treated fiber.
  • a process for producing water-insoluble artificial casein fiber which comprises the steps of impregnating hardened fiber, prepared from acaseln solution by a spinning and hardening process, with a solution of a water-soluble salt 'of chromic acid, and then treating the impregnated fiber with a solution of a reducing agent.
  • a process for producing water-insoluble artificial casein fiber which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinning and hardening process, with a solution of an alkali metal bichromate, and then treatin the impregnated fiber with a solution of an alkali metal bisulphite.
  • Water-insoluble artificial casein fiber comprising an insolubilized fiber body prepared from a casein solution by a spinning and hardening process, and containing a subsequently-incorporated water-insoluble chromium compound in and on said fiber body, said fiber possessing improved dynamometric resistance and improved fastness to boiling water, milling, washing and dyeing, as compared with the same insolubilized artificial fiber free from said water-insoluble chromium compound.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)

Description

Patented Sept. 2, 1947 UNITED STATESPATENT OFFICE PROCESS FOR IMPROVING THE PROPER.
TIES OF WATER-INSOLUBLE ARTIFICIAL PROTEIN FIBRES Giampiero Comolli, Milan, Italy, assig'nor to Sandoz A. G., Basel, Switzerland No Drawing. Application November 8, 1939. Serial No. 303,158. In Italy November 14, 1938 pounds, there is a very appreciable improvement in the dynamometric resistance of the fibre itself (in the moist as well as in the dry state),
in the resistance to fulling, friction and wear,'
in the resistance to the action of boiling water even in the presence of acid or alkali and also in the resistance to the action of hot iron (ironing), and thereis also an increase in the fastness of the dyeings produced thereon with acid dyestufis and chrome dyestufls as well as with direct dyestufis and dyestufis belonging to other categories.
The artificial fibre, when subjected to the treatment hereinafter described, undergoes an action similar to the action produced on depilated skins when subjected to chrome tanning with one or two immersions, which acquire great tenacity and powerful resistance to stretching and are not affected by boiling water.
This treatment enables, furthermore. the above-mentioned artificial fibres to absorb and retain dyestuffs in a much higher condition of stability than is the case with artificial fibres obtained from protein-Hike material not subjected to the process which forms the subject matter of the patent. In fact, acid dyestufis which when applied on untreated fibres do not resist even light washing, on the contrary after treatment according to the present invention they withstand very well washing at 60C. in presence of soap and carbonate of soda; Moreover, the
treatment in question makes it possible to dye ,with all chrome dyestuffs generally without impairing the resistance of the artificial fibre, contrary to what happens in the case of dyed fibres obtained from protein-like substances and not treated by the process which forms the subject matter of this invention.
The treatment which is covered by this invention and can be used in the actual manufacture of artificial fibres formed of or containing protein-like substances, is based on the use of salts of chromium (chrome alum, chromium sulphate,
chromium chloride, etc., either normal or of vari-- ous degrees of basicity). Ii desired the treatment may be effected with two baths, the first containing for example sodium or potassium bichromate and the other containing products capable of converting the compounds of chromic anhydride into compounds of chromium sesquioxide.
In the preparation of this second bath the following compounds can be used:
(a) Sodium thiosulphate, sodium bisulphite, sulphurous acid and its derivatives or any other reducing means or substance.
(b) Any oxidising means or substance capable of converting chromic acid into perchromic acid which, owing to its instability. can produce compounds of chromium sesquioxide.
The following examples illustrate how the invention may be carried out in practice, but it is to be understood that the invention is in no way limited by the details given in these examples.
Example 1 Artificial fibre prepared from casein is impregnated in a bath containing grams per litre of potassium bichromate with the addition, if desired, of a mineral acid. After the impregnation of the fibre it is squeezed and placed in another bath containing 100 grams per litre of sodium bisulphite and then thoroughly washed with water. The fibre so treated acquires all the properties above mentioned (better resistance to stretching, wear, boiling water, etc.).
Example 2 Artificial fibre treated as in Example 1 is dyed with chrome dyes by the afterchroming process as well as in the dyeing process with a single bath.
The alkaline iulling of the dyed material does not exercise any negative influence upon the shade and the resistance of the fibres, whilst similar dyeings executed on untreated fibre are practically unusable after having been subjected to alkaline fulling.
. fully washed out.
acaaem Example 4 Artificial casein fibre is soaked in a 10% aque-. ous sodium bichromate solution at 35 C. until bisulphite, the sodium hydrosulphite, thiosulphate or gaseous sulphurous acid mixed with steam.
' Example 100 parts or casin staple fibres are treated in a milling drum during minutes with a 30-40" C. warm solution of 8.10.D ,s of sodiumor potassium bichromate in 400-500 parts of water.
,Thereon-4 parts of hydrochloric acid or a corresponding quantity of sulphuric'acid are added thereto in order to liberate the chromic acid.
. After 20 minutes the major part of the chromic acid has been taken up by. the fibre and the solution is coloured only weakly yellow. For the reduction, thereis added a solution of 12-45 parts of sodium bisulphite and the drum allowed to run until the green solution becomes almost colorless. The fibres are then'rinsed, treated with some ammonia or another alkali like soda, etc., in order to neutralize the free acid, and care- Eaiample 6 The textile material subjected to suchtreatment can then be dyed with any desired dyestuffs. Acid and chrome dyestufi's dye casein and animal fibres, whereassubstantive dyestufl's dye casein and cellulosic fibres; therefore, any desiredcombination of shade may be produced.
The textile materlaltreated and dyed according to the example possesses a much better touch and better dynamometric properties as compared with the material that has not been subjected to the tanning operation.
Example 7 100 parts of casein yam are treated during 18 hours at ?"C. in a solution of the following composition:
Parts Water '1000 Chrome alum 120' Anhydrous sodium carbonate 12 and if necessary 3 partsof a wetting agent which is resistant to chrome salts. j
After this treatment the yarn is hydroextracted, washed out, treated during 21 minutes in 1000 parts of water containing 2 parts of concentrated ammonia, washed again, hydroextracted and dried.
The casein fibre which is colored in a clear olive green shade possesses a smooth touch which remains, even after a subsequent dyeing in a bath containing mineral acid. The resistance to breaking and the elasticity of the casein fibre treated in this manner is much better as compared with the casein fibre which has not been subjected to the above treatment.
What I claim is:
1. A process for producin water-insoluble artificial casein fiber, which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinnin and hardening process, with a solution of a water-soluble chromium'compound, and then converting the latter,
into a. water-insoluble chromium compound by treatment of the impregnated fiber with a reducing agent, thereby causing the formation and fixation of the water-insolubl chromium compound in and on the treated fiber.
2. A process for producing water-insoluble artificial casein fiber, which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinning and hardening process, with a solution of a water-soluble salt of chromic acid, and then converting the latter into a water-insolubble chromium compound by treatment of the impregnated fiber with a reducing agent, thereby causing the formation and fixation of the water-insoluble chromium compound in and on the treated fiber. I
3. A process for producing water-insoluble artificial casein fiber, which comprises the steps of impregnating hardened fiber, prepared from acaseln solution by a spinning and hardening process, with a solution of a water-soluble salt 'of chromic acid, and then treating the impregnated fiber with a solution of a reducing agent.
4. A process for producing water-insoluble artificial casein fiber, which comprises the steps of impregnating hardened fiber, prepared from a casein solution by a spinning and hardening process, with a solution of an alkali metal bichromate, and then treatin the impregnated fiber with a solution of an alkali metal bisulphite.
5. Water-insoluble artificial casein fiber comprising an insolubilized fiber body prepared from a casein solution by a spinning and hardening process, and containing a subsequently-incorporated water-insoluble chromium compound in and on said fiber body, said fiber possessing improved dynamometric resistance and improved fastness to boiling water, milling, washing and dyeing, as compared with the same insolubilized artificial fiber free from said water-insoluble chromium compound.
GIAMPIERO COMOLLI.
REFERENCES crr n The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 77,990 Lowrey May 19, 1868 625,345 Millar Oct. 15, 1898 836,788 Todtenhaupt Nov. 2'7, 1906 950,435 Chavassieu Feb. 22, 1910 1,865,497 Atwood July 5, 1932 2,103,163 Lange Dec. 21, 1937 2,120,851 1 Becker et al June 14, 1938 2,140,274 Whittier et a1 Dec. 13, 1938 2,169,955 oosterbeek et a1. Aug, 15, 1939 1,968,991 Clickner Aug. 7, 1934 2,046,320 Burbank July 7, 1936 FOREIGN PATENTS Number Country Date 467,812 Great Britain June 22, 1937 372,271 Italy June 22, 1939 France Nov. 29, 1905
US303158A 1938-11-14 1939-11-06 Process for improving the properties of water-insoluble artificial protein fibres Expired - Lifetime US2426861A (en)

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IT536088X 1938-11-14
CH536104X 1939-01-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926061A (en) * 1957-04-23 1960-02-23 Varsenig Z Pasternak Method of increasing the curl, filling power, etc., of land fowl feathers with zirconium sulfate and product produced thereby
US2928713A (en) * 1957-04-23 1960-03-15 Varsenig Z Pasternak Chromic acid treatment of feathers
US3098696A (en) * 1959-08-18 1963-07-23 American Cyanamid Co Manufacture of sterile surgical suture collagen

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2533356A (en) * 1948-02-06 1950-12-12 Borden Co Casein filaments treated with mercuric salt and formaldehyde solution
NL80704C (en) * 1954-05-24
US3314743A (en) * 1963-11-07 1967-04-18 Gagliardi Domenick Donald Processes for treatment of preformed articles of olefin polymers and resulting products

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US77990A (en) * 1868-05-19 Improved mode of treating leather, cloth, and the like
US625345A (en) * 1899-05-23 Adam millar
FR356404A (en) * 1905-07-25 1905-11-29 Friedrich Todtenhaupt Manufacturing process of artificial yarns for silks, horsehair and fabrics
US836788A (en) * 1905-07-17 1906-11-27 Friedrich Todtenhaupt Production of artificial silk and artificial hair from casein.
US950435A (en) * 1908-12-22 1910-02-22 Henri Louis Joseph Chavassieu Process of obtaining proteo-cellulosic products.
US1865497A (en) * 1926-04-30 1932-07-05 Technicolor Method of hardening gelatine films and surfaces and resulting product
US1968991A (en) * 1933-01-30 1934-08-07 Kraft Phenix Cheese Corp Manufacture of transparent sheets or coatings
US2046320A (en) * 1934-10-25 1936-07-07 Technicolor Motion Picture Method of making hardened gelatin films and resulting product
GB467812A (en) * 1935-10-22 1937-06-22 Albert Charles Chibnall Improvements in or relating to the production of artificial filaments, threads, films and the like
US2103163A (en) * 1935-04-25 1937-12-21 Firm Carl Freudenberg G M B H Process for rendering fibers or threads from animal collagen ironproof
US2120851A (en) * 1934-09-19 1938-06-14 Freudenberg Carl Gmbh Process for the manufacture of spun goods, fabrics, and other textiles
US2140274A (en) * 1937-08-12 1938-12-13 Earle O Whittler Fiber
US2169955A (en) * 1937-05-11 1939-08-15 American Enka Corp Treatment of casein fibers

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US77990A (en) * 1868-05-19 Improved mode of treating leather, cloth, and the like
US625345A (en) * 1899-05-23 Adam millar
US836788A (en) * 1905-07-17 1906-11-27 Friedrich Todtenhaupt Production of artificial silk and artificial hair from casein.
FR356404A (en) * 1905-07-25 1905-11-29 Friedrich Todtenhaupt Manufacturing process of artificial yarns for silks, horsehair and fabrics
US950435A (en) * 1908-12-22 1910-02-22 Henri Louis Joseph Chavassieu Process of obtaining proteo-cellulosic products.
US1865497A (en) * 1926-04-30 1932-07-05 Technicolor Method of hardening gelatine films and surfaces and resulting product
US1968991A (en) * 1933-01-30 1934-08-07 Kraft Phenix Cheese Corp Manufacture of transparent sheets or coatings
US2120851A (en) * 1934-09-19 1938-06-14 Freudenberg Carl Gmbh Process for the manufacture of spun goods, fabrics, and other textiles
US2046320A (en) * 1934-10-25 1936-07-07 Technicolor Motion Picture Method of making hardened gelatin films and resulting product
US2103163A (en) * 1935-04-25 1937-12-21 Firm Carl Freudenberg G M B H Process for rendering fibers or threads from animal collagen ironproof
GB467812A (en) * 1935-10-22 1937-06-22 Albert Charles Chibnall Improvements in or relating to the production of artificial filaments, threads, films and the like
US2169955A (en) * 1937-05-11 1939-08-15 American Enka Corp Treatment of casein fibers
US2140274A (en) * 1937-08-12 1938-12-13 Earle O Whittler Fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926061A (en) * 1957-04-23 1960-02-23 Varsenig Z Pasternak Method of increasing the curl, filling power, etc., of land fowl feathers with zirconium sulfate and product produced thereby
US2928713A (en) * 1957-04-23 1960-03-15 Varsenig Z Pasternak Chromic acid treatment of feathers
US3098696A (en) * 1959-08-18 1963-07-23 American Cyanamid Co Manufacture of sterile surgical suture collagen

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Publication number Publication date
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FR855286A (en) 1940-05-07
GB536104A (en) 1941-05-02
GB536088A (en) 1941-05-02
NL60511C (en)
US2368690A (en) 1945-02-06

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