EP0592979A1 - Procédé de modification de poils d'animaux - Google Patents

Procédé de modification de poils d'animaux Download PDF

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Publication number
EP0592979A1
EP0592979A1 EP93116409A EP93116409A EP0592979A1 EP 0592979 A1 EP0592979 A1 EP 0592979A1 EP 93116409 A EP93116409 A EP 93116409A EP 93116409 A EP93116409 A EP 93116409A EP 0592979 A1 EP0592979 A1 EP 0592979A1
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EP
European Patent Office
Prior art keywords
plasma
argon
wool
helium
sample
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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.)
Ceased
Application number
EP93116409A
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German (de)
English (en)
Inventor
Tomiji Wakida
Kouichi Murai
Hiroshi Uchiyama
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Ec Chemical Co Ltd
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Ec Chemical Co Ltd
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Publication date
Application filed by Ec Chemical Co Ltd filed Critical Ec Chemical Co Ltd
Publication of EP0592979A1 publication Critical patent/EP0592979A1/fr
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B19/00—Treatment of textile materials by liquids, gases or vapours, not provided for in groups D06B1/00 - D06B17/00
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk

Definitions

  • the present invention relates to a process for modifying animal hair or a product thereof by a plasma treatment at atmospheric pressure.
  • the process of the present invention is very simple and enables the significant improvement of the dyeability and shrinkage in washing, of animal hair or a product thereof.
  • Each animal hair such as wool or the like is hair covering each animal body and has such features that it has softness, curl and a high water-retaining property and, when made into textile products, has a high space ratio and an excellent heat-retaining property. Hence, it is in wide use as clothes.
  • Each animal hair has, on the surface, flakes called "cuticle" as shown in Fig. 1 (1 is a cuticle). (This is a big feature of animal hair.) Since the surface of each cuticle 1 is highly hydrophobic, the dyeing of animal hair is said to proceed in such a manner that a dye enters into the hair gradually through each gap 2 between the cuticles and the hair is dyed.
  • the high hydrophobicity of the surface of animal hair requires a high temperature and/or a long time in dyeing the hair.
  • the dyeing of animal hair at high temperatures allows the resulting animal hair product to have impaired touch. Hence, a technique for dyeing at low temperatures has been hitherto sought.
  • Wool further has a problem of shrinkage in washing. Untreated wool or wool products cause shrinkage in washing, and the shrinkage reaches 30 % or more in the case of Viyella® (a wool product).
  • One of the present inventors previously proposed a process for plasma-treating the surface of a plastic film or a synthetic fiber to impart high hydrophilicity to said surface, which process comprises placing a plastic film or a synthetic fiber in a plasma generator and generating a plasma in the generator at atmospheric pressure by glow discharge to subject the surface of the plastic film or the synthetic fiber to plasma treatment (Japanese Patent Application No. 187215/1990 and USP 5124173).
  • the present inventors made further study on the above process and completed the present process capable of modifying animal hair remarkably.
  • a process for modifying animal hair or a product thereof comprises placing animal hair or a product thereof between two electrodes facing each other, in a plasma generator, introducing a plasma-excitable gas into the plasma generator and applying a high voltage of high frequency between the electrodes at atmospheric pressure to subject the gas to plasma excitation to give rise to glow discharge between the electrodes.
  • FIG. 2 An example of the plasma generator used in the present invention is shown in Fig. 2.
  • a wool cloth 2 is placed between two electrodes 1 facing each other.
  • a dielectric substance 3 such as glass, ceramic, polyimide film or the like is placed on the upper and/or lower electrode in order to prevent spark discharge during plasma excitation.
  • a plasma-excitable gas e.g. a mixture of argon and helium
  • a high voltage of high frequency e.g. 3,000 Hz and 4,200 V
  • a high voltage of high frequency e.g. 3,000 Hz and 4,200 V
  • FIG. 2 is an example showing the principle of the atmospheric pressure plasma generator of the present invention
  • an apparatus enabling a semi-continuous or continuous operation may be used as necessary.
  • FIG. 3 shows an example of the apparatus for semi-continuous operation.
  • a belt-shaped wool cloth is fed through a slit 6.
  • a shutter 7 is closed to prevent the outflow of the gas and the inflow of air, and glow discharge is initiated to conduct a plasma treatment.
  • the shutter 7 is opened; the cloth is moved forward by the length of electrodes; the shutter 7 is reclosed and the same treatment is repeated.
  • a continuous operation (a continuous treatment) is possible by, for example, narrowing the diameter of the slit 6 and keeping the plasma-excitable gas inside the apparatus, at a pressure higher than atmospheric pressure.
  • plasma-excitable gas refers to a gas which is plasma-excitable when it is placed between two electrodes facing each other in an atmospheric pressure plasma generator and when a high voltage of high frequency is applied between the electrodes.
  • a plasma-excitable gas is exemplified by argon, helium, neon, cryptone, xenon, nitrogen, CO2, flon gases (e.g. CF4) and mixtures thereof.
  • the gas may be used in combination with a ketone, a lower hydrocarbon gas, or other organic compound gas of relatively low boiling point as necessary for stabilization of glow discharge, etc. as long as the effect of the present invention is not impaired.
  • the plasma-excitable gas contains preferably argon and/or helium, more preferably argon and helium.
  • the plasma-excitable gas is a mixture of argon and helium wherein the proportions of argon and helium are 80-10 parts by volume and 20-90 parts by volume, preferably 70-30 parts by volume and 30-70 parts by volume.
  • the plasma-excitable gas contains preferably argon and/or helium and a ketone, more preferably argon and a ketone.
  • the plasma-excitable gas is a mixture of argon and a ketone wherein the proportions of argon and the ketone are 99.99-95 parts by volume and 0.01-5 parts by volume, preferably 99.9-99 parts by volume and 0.1-1 part by volume.
  • the ketone as a component of the plasma-excitable gas used in the present invention is preferably selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone. Acetone is most preferable.
  • the high voltage of high frequency applied between two electrodes in the present invention to conduct plasma excitation at atmospheric pressure is appropriately set depending upon, for example, the properties of animal hair or a product thereof to be treated.
  • a voltage of 1,000-8,000 V, preferably 1,000-5,000 V is used.
  • the frequency of electric source used is 500-100,000 Hz, preferably 1,000-10,000 Hz.
  • animal hair refers to hair-covered mammals such as sheep, goat, rabbit and the like.
  • Animal hair can be exemplified by wool, hair of Angola rabbit and hair of Kashmir goat.
  • Animal hair product includes not only products made of animal hairs alone but also products made of mixtures between animal hair and other fiber (e.g. synthetic fiber), and can be exemplified by a cloth, a woven cloth, a knitted goods, an unwoven cloth and a loose fiber.
  • the surface of animal hair is easily endowed with high hydrophilicity.
  • the degree of dye exhaustion in animal hair or product thereof is increased, and a shorter dyeing time and a lower dyeing temperature can be employed.
  • the shrinkage in washing, of animal hair or product thereof is improved significantly.
  • a tropical was subjected to complete fat removal in a Soxhlet's extractor using toluene and ethanol as an extraction solvent, followed by through washing with water and drying to prepare a sample cloth.
  • the wool cloth was treated as above for 10, 30, 60 and 180 seconds to obtain four treated cloths. Onto each of the treated cloths was dropped 6 ⁇ l of distilled water, and there was measured a time in which the water began to infiltrate into each treated cloth. The results were as follows.
  • Example 1 The procedure of Example 1 was repeated with the exception that the mixed gas used in Example 1 was replaced by a mixed gas obtained by adding about 5 ppm of acetone to argon (this mixed gas consisted of about 99.7 parts by volume of argon and 0.3 part by volume of acetone). The results were as follows.
  • the treated wool cloths showed improvement in hydrophilicity as compared with the untreated wool cloth.
  • Wool was placed in a Soxhlet's extractor and subjected to wool fat removal using toluene and ethanol.
  • the resulting wool was placed between two electrodes in a reaction vessel shown in Fig. 2.
  • the air inside the vessel was replaced by a mixed gas consisting of equal volumes of argon and helium.
  • a voltage of 3,000 Hz and 3,000 V was applied between the two electrodes, whereby glow discharge was allowed to appear and the wool was subjected to a plasma treatment. The treatment was conducted for 30 seconds and the treated wool was taken out to obtain a sample (1).
  • each of the untreated sample (wool subjected to no plasma treatment), the sample (1) and the sample (2) was dyed in a dyeing bath of 60°C to measure the dye uptake with the lapse of dyeing time.
  • the results are shown in Table 1.
  • the dye used was Brilliant Scarlet 3R, which was an acid dye of levelling type, and the dyeing bath was prepared by adding 0.1 mole, per liter of water of KH2PO4 and the same amount of Na2HPO4 (buffer) to control the bath pH at 4.5.
  • the sample (1) which was subjected to an atmospheric pressure plasma treatment using a mixed gas consisting of equal volumes of argon and helium, was dyed in a shortest time.
  • the sample (2) which was subjected to the same atmospheric pressure plasma treatment using a mixed gas consisting of argon and acetone, was dyed in a longer time.
  • the present process increases dye uptake and decreases dyeing time. It is not necessary to increase dyeing temperature for higher efficiency. This low dyeing temperature is advantageous because it does not impair the touch of wool. These meritorious effects of the present process are epoch-making.
  • Viyella® (a wool product) not subjected to shrink-resistant finish was cut to prepare six samples each of 100 mm x 100 mm.
  • the two samples were not treated and were used for comparison.
  • the other four samples were each subjected to a plasma treatment as follows.
  • a glass plate as dielectric substance of 180 mm x 240 mm x 1 mm (thickness) was laminated onto each of upper and lower electrodes of 150 mm x 200 mm placed in an atmospheric pressure plasma reaction vessel; the distance between the two electrodes was set at 8 mm; a wool cloth (one of the above four samples) was placed between the electrodes and subjected to a plasma treatment by atmospheric pressure glow discharge, wherein the composition of the gas used and the treating time were as follows.
  • the voltage applied was 3,000 Hz and 3,000 V.
  • Example 3 The same wool fiber as used in Example 3 was placed between two Electrodes in an atmospheric pressure plasma reaction vessel shown in Fig. 1 (?); in this reaction vessel, glow discharge was allowed to appear between the electrodes by applying a high voltage of high frequency (1,000 Hz and 3,400 V) in a mixed gas consisting of 40 parts by volume of argon and 60 parts by volume of helium; thereby, the wool fiber was subjected to a plasma treatment.
  • the resulting wool fiber was put in an acidic dyeing bath of 60°C and the dyed fiber was compared with the untreated fiber.
  • the acidic dyeing bath was prepared by using a milling dye (Kayanol Cyanine Blue 6B manufactured by Nippon Kayaku Co., Ltd.) and controlling the bath pH at 5.5.
  • the dye uptake i.e. [(moles of dye adhered onto fiber)/(g of fiber)] x 106 with the lapse of dyeing time was as shown in Table 4.
  • Table 4 Sample Dye uptake 12 hr 24 hr 36 hr 48 hr Untreated 3.9 5.2 6.1 6.5 Treated 6.4 9.2 12.0 14.4
  • the time of half dyeing (t 1/2 ) was 22,245 min in the case of the untreated wool fiber and 9,057 min in the case of the treated sample. Thus, the dyeing time of the treated sample was less than half of that of the untreated sample.
  • Example 5 The same dyeing test as in Example 5 was conducted using Orange II which was an acid dye of levelling type.
  • the dyeing bath pH was 4.5.
  • a mixed gas consisting of 99.5 parts by volume of argon and 0.5 part by volume of acetone was used; a voltage of 5,000 Hz and 2,600 V was applied; the other conditions were the same as in Example 1.
  • the dye uptake i.e. [(moles of dye adhered onto fiber)/(g of fiber)] x 106 with the lapse of dyeing time was as shown in Table 5.
  • Table 5 Sample Dye uptake 10 min 20 min 30 min 40 mi 50 min Untreated 3.4 4.9 6.2 7.0 7.2 Treated 5.5 7.5 9.0 10.0 10.0
  • the time of half dyeing was 42 min in the case of the untreated wool fiber and 18 min in the case of the treated wool fiber.
  • the dyeing time of the treated sample was less than half of that of the untreated sample.
  • a tropical not subjected to shrink-resistant finish was cut to prepare six samples of the same size as in Example 4. Each of them was subjected to a plasma treatment using the same apparatus as in Example 4, to prepare the following samples 1-5.
  • Gas composition Treating time Resulting sample Argon 50 parts by volume 60 seconds 1
  • Helium 50 parts by volume Same as above 180 seconds 2
  • Argon 99.8 parts by volume 60 seconds 3
  • Acetone 0.2 part by volume Same as above 180 seconds 4 Not treated 5 (for comparison)
  • the voltage applied was 3,000 Hz and 3,300 V.
  • the treating time was 30 seconds for the back side of each sample and 90 seconds for the front side.
  • Shrinkage in washing was improved by a plasma treatment, also in the case of tropical.
  • An argon-acetone mixed gas gave a better result than an argon-helium mixed gas,also in this Example.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Coloring (AREA)
  • Plasma Technology (AREA)
EP93116409A 1992-10-13 1993-10-11 Procédé de modification de poils d'animaux Ceased EP0592979A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP299103/92 1992-10-13
JP4299103A JPH06123062A (ja) 1992-10-13 1992-10-13 獣毛の改質法

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EP0592979A1 true EP0592979A1 (fr) 1994-04-20

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JP (1) JPH06123062A (fr)
KR (1) KR940009413A (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2711680A1 (fr) * 1993-10-27 1995-05-05 Maupu Entr Pompes Procédé de blanchiment et d'amélioration de la tenue des teintures sur les matières organiques.
EP0826814A2 (fr) * 1996-08-28 1998-03-04 Siegfried Dr. Strämke Procédé et appareil pour le traitement des matériaux fibreux
ES2270710A1 (es) * 2005-06-15 2007-04-01 Consejo Superior Investig. Cientificas Tratamiento de fibras de lana o queratinas y sus mezclas con otras fibras y/o sus productos mediante post-descarga de plasma.
ITMI20100234A1 (it) * 2010-02-16 2011-08-17 Giorgio Rovero Processo di tintura a stoccaggio (pad-batch) di articoli tessili comprendente una fase di trattamento con gas ionizzato o plasma
DE102011010273A1 (de) 2011-02-02 2012-08-02 Cinogy Gmbh Verfahren zur Behandlung von menschlichem oder tierischem Haar und Gerät zur Durchführung des Verfahrens
US8309033B2 (en) 2003-05-05 2012-11-13 Commonwealth Scientific And Industrial Research Organisation Plasma treatment apparatus and method
WO2013140371A1 (fr) * 2012-03-22 2013-09-26 Ariel-University Research And Development Company, Ltd. Procédés pour traiter des fibres kératiniques et utilisations correspondantes
WO2016102972A3 (fr) * 2014-12-23 2016-09-15 Jemella Limited Procédé et appareil de manipulation de la forme des cheveux
IT201900009348A1 (it) * 2019-06-18 2020-12-18 Vebachem Srls Processo tintoriale tessile comprendente l’uso di coloranti naturali purificati impiegati nel settore alimentare e corrispondente uso nella tintoria tessile di coloranti naturali purificati derivati dal settore alimentare

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632299A (en) * 1969-09-19 1972-01-04 Us Agriculture Shrinkproofing of animal fibers by passing said through an electrical discharge zone containing ozone
EP0467639A2 (fr) * 1990-07-17 1992-01-22 E.C. Chemical Co. Ltd. Procédé de traitement de surface au plasma sous pression atmosphérique
EP0548013A1 (fr) * 1991-12-16 1993-06-23 Ciba-Geigy Ag Procédé de teinture de la laine avec l'aide d'un pétraitement avec un plasma basse température ou Corona

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632299A (en) * 1969-09-19 1972-01-04 Us Agriculture Shrinkproofing of animal fibers by passing said through an electrical discharge zone containing ozone
EP0467639A2 (fr) * 1990-07-17 1992-01-22 E.C. Chemical Co. Ltd. Procédé de traitement de surface au plasma sous pression atmosphérique
US5124173A (en) * 1990-07-17 1992-06-23 E. C. Chemical Co., Ltd. Atmospheric pressure plasma surface treatment process
EP0548013A1 (fr) * 1991-12-16 1993-06-23 Ciba-Geigy Ag Procédé de teinture de la laine avec l'aide d'un pétraitement avec un plasma basse température ou Corona

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HOLLAHAN J.R. ET AL.: "Techniques and applications of plasma chemistry", 1974, WILEY INTERSCIENCE, NEW-YORK; USA *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2711680A1 (fr) * 1993-10-27 1995-05-05 Maupu Entr Pompes Procédé de blanchiment et d'amélioration de la tenue des teintures sur les matières organiques.
EP0826814A2 (fr) * 1996-08-28 1998-03-04 Siegfried Dr. Strämke Procédé et appareil pour le traitement des matériaux fibreux
EP0826814A3 (fr) * 1996-08-28 1998-08-05 Siegfried Dr. Strämke Procédé et appareil pour le traitement des matériaux fibreux
US8309033B2 (en) 2003-05-05 2012-11-13 Commonwealth Scientific And Industrial Research Organisation Plasma treatment apparatus and method
ES2270710A1 (es) * 2005-06-15 2007-04-01 Consejo Superior Investig. Cientificas Tratamiento de fibras de lana o queratinas y sus mezclas con otras fibras y/o sus productos mediante post-descarga de plasma.
ITMI20100234A1 (it) * 2010-02-16 2011-08-17 Giorgio Rovero Processo di tintura a stoccaggio (pad-batch) di articoli tessili comprendente una fase di trattamento con gas ionizzato o plasma
WO2011101780A1 (fr) 2010-02-16 2011-08-25 Giorgio Rovero Procédé de teinture continue comprenant le foulardage de mélanges de fibres animales et textiles fabriqués à partir dudit procédé
DE102011010273A1 (de) 2011-02-02 2012-08-02 Cinogy Gmbh Verfahren zur Behandlung von menschlichem oder tierischem Haar und Gerät zur Durchführung des Verfahrens
WO2012103877A1 (fr) 2011-02-02 2012-08-09 Cinogy Gmbh Procédé de traitement de cheveux humains ou de poils d'animaux et appareil permettant de mettre en œuvre le procédé
US9038645B2 (en) 2011-02-02 2015-05-26 Cinogy Gmbh Method for treating human or animal hair and apparatus for carrying out the method
WO2013140371A1 (fr) * 2012-03-22 2013-09-26 Ariel-University Research And Development Company, Ltd. Procédés pour traiter des fibres kératiniques et utilisations correspondantes
WO2016102972A3 (fr) * 2014-12-23 2016-09-15 Jemella Limited Procédé et appareil de manipulation de la forme des cheveux
CN107105850A (zh) * 2014-12-23 2017-08-29 洁美来有限公司 用于控制毛发形状的方法及设备
US10716381B2 (en) 2014-12-23 2020-07-21 Jemella Limited Method and apparatus for manipulating the shape of hair
US11771192B2 (en) 2014-12-23 2023-10-03 Jemella Limited Method and apparatus for manipulating the shape of hair
IT201900009348A1 (it) * 2019-06-18 2020-12-18 Vebachem Srls Processo tintoriale tessile comprendente l’uso di coloranti naturali purificati impiegati nel settore alimentare e corrispondente uso nella tintoria tessile di coloranti naturali purificati derivati dal settore alimentare

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Publication number Publication date
JPH06123062A (ja) 1994-05-06
KR940009413A (ko) 1994-05-20

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