EP1176245B1 - Fibres animales non-rétrécissantes - Google Patents

Fibres animales non-rétrécissantes Download PDF

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Publication number
EP1176245B1
EP1176245B1 EP20010117262 EP01117262A EP1176245B1 EP 1176245 B1 EP1176245 B1 EP 1176245B1 EP 20010117262 EP20010117262 EP 20010117262 EP 01117262 A EP01117262 A EP 01117262A EP 1176245 B1 EP1176245 B1 EP 1176245B1
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Prior art keywords
fiber
animal fiber
wool
ozone
animal
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German (de)
English (en)
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EP1176245A1 (fr
Inventor
Hisashi Ichimura
Ryo Umehara
Tadashi Karakawa
Kunihiro c/o Kurabo Industries Ltd Oshima
Kazuhiro c/o Kurabo Industries Ltd Nakase
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Kurabo Industries Ltd
Kurashiki Spinning Co Ltd
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Kurabo Industries Ltd
Kurashiki Spinning Co Ltd
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Priority claimed from JP2001057004A external-priority patent/JP3722708B2/ja
Application filed by Kurabo Industries Ltd, Kurashiki Spinning Co Ltd filed Critical Kurabo Industries Ltd
Priority to EP20010117262 priority Critical patent/EP1176245B1/fr
Publication of EP1176245A1 publication Critical patent/EP1176245A1/fr
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    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/196—Percarboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/02—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fibres, slivers or rovings
    • 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
    • D06M11/00—Treating 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
    • D06M11/32—Treating 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
    • D06M11/34—Treating 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 oxygen, ozone or ozonides
    • 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
    • D06M11/00—Treating 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
    • D06M11/32—Treating 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
    • D06M11/50—Treating 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 hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • 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
    • D06M11/00—Treating 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
    • D06M11/51—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/54—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

  • the present invention relates to an animal fiber to which shrink proofing and pilling resistance are given, and a method for preparation thereof. More specifically, the present invention relates to an animal fiber to which shrink proofing and pilling resistance are given without impairing a superior water repellent property that animal fibers originally possess and a method for preparation thereof.
  • Animal fiber is peculiar natural fiber having specific hand-feeling texture depending on sheep breeds, revealing bio-degradability, having various excellent properties such as hygroscopicity, moisture-releasing property, heat retaining property, flame retardancy and dyeing property, and further, water-repellency. It is special fiber which has appropriate fiber strength and elongation permissible for wear and higher abrasion resistance, also from the standpoint of fiber mechanical properties, and has been esteemed for long time.
  • felting property in aqueous washing and pilling property in wear derived from a cuticle tissue structure of animal fiber are undesirable natures as apparel wear. Therefore, studies for improving the surface have been long effected mainly on shrink proofing, and pilling resistant work has also been conducted along with the studies.
  • any of animal fiber obtained like this is an improving method sacrificing the water repellency which is an inherent nature of animal fiber.
  • a water repellent membrane of animal fiber is an organization for exerting an influence on hygroscopicity and moisture releasing property and for controlling heat transfer accompanied by adsorption and desorption of water, and exerts an influence on heat retaining property and comfortability.
  • the conventional shrink proofing product can prevent shrink by aqueous washing, but lacks in heat retaining property and comfortability.
  • Japanese Patent Kokai No. 126997/1975 discloses a method in which dyeing property and shrink proofing of wool and pilling resistance of a wool-synthetic fiber blended product are improved without deteriorating hand-feeling and fiber strength of wool according to a procedure in which wool sliver is impregnated with an aqueous solution of acids or acidic salts and drained by squeezing rolls, and is placed in a sealed chamber previously filled with an ozone-containing gas having an ozone concentration of 35.5 mL/L, and further, treated at 50°C for 10 minutes while feeding a new ozone-containing gas.
  • this method carries out only oxidation into a cystine crosslinked bond (-S-S-) which performs main role of wool shrink proofing, and no reduction treatment is conducted.
  • a -S-S-bond is not cleaved until this reduction treatment and this cleavage gives satisfactory shrink proofing to wool, therefore, sufficient shrink proofing and pilling resistance can not be obtained by the disclosed method.
  • the above-mentioned methods is conducted in a sealed system since the treatment should be conducted in an ozone gas atmosphere, and exposure is effected with the aid of molecular movement of an ozone gas, therefore, when the amount of wool treating is increased, unevenness of an ozone gas exposure can not be avoided, and this directly produces a unevenness treatment and uniform wool shrink proofing and dyeing are not obtained.
  • the productivity is low due to the sealed system treatment, and when an ozone gas leaks directly out of the treating apparatus, deterioration in working environment and environmental charge are large, and industrialization is difficult.
  • Japanese Patent Kokai No. 142759/1980 discloses a method and an apparatus in which fiber is treated with an ozone-steam mixed material.
  • worsted knitted fabric made of keratinous animal fiber is suspended on a belt conveyor circulating in a special treatment apparatus equipped with an exhaust apparatus, steam is introduced in this apparatus to increase the temperature to 79°C, a fan is started to introduce an ozone-air mixed gas (ozone introduction amount: 3.4 g/minute) and this mixed gas retained in the apparatus for 8.25 minutes to impart shrink proofing.
  • ozone introduction amount: 3.4 g/minute ozone introduction amount: 3.4 g/minute
  • this mixed gas retained in the apparatus for 8.25 minutes to impart shrink proofing.
  • only ozone oxidation is conducted, and no reduction treatment is effected. Therefore, the imparted shrink proofing is not satisfactory, and further, an ozone gas tends to leak due to the defective construction of apparatus, inviting deterioration in working environment.
  • Japanese Patent Kokai No. 19961/1991 discloses a method of shrink proofing of animal fiber using ozone as an oxidizer. It describes that an ozone gas is passed through a glass filter to give fine bubbles, in a water bath, and this bubbles are allowed to contact animal fiber. But bubbles generated through a glass filter or the like are too large to render ozone gas bubbles to reach fine portions in a fiber assembly, and treat only the surface of the fiber assembly.
  • Japanese Patent Kokai No. 72762/1998 discloses a method in which fiber is immersed in the form of tow, thread, fabric, knit fabric and the like into a water-dissolved ozone prepared by dispersing in water an ozone-containing gas composed of ozone and oxygen or air in the form of bubbles having a diameter of 0.08 mm or less. It describes a method in which an ozone-containing gas is introduced in water to form bubbles, this bubbles are broken by allowing it to collide against small walls in a line mixer when it passes through the line mixer, to give fine bubbles having a diameter of 0.08 mm or less showing enhanced solubility in water, for obtaining ozone dissolved in water having high concentration. This is merely a method for treating rayon and other fiber using ozone in dissolved in water.
  • the present invention provides an animal fiber to which high shrink proofing and pilling resistance are simultaneously given without impairing its water repellence. Moreover, the present invention also provides a method for preparation of the animal fiber in which a chemical not containing toxic chlorine is used from the view point of environmental preservation.
  • the present invention relates to an animal fiber which is superior in shrink proofing and pilling resistance, and maintains a water repellent property that animal fibers originally possess.
  • the present invention relates to the animal fiber wherein the shrink proofing is set to an area shrinkage rate of not more than 8 % in a three-hours aqueous washing, when measured as a felting shrinkage rate in conformity with a WM TM 31 method (Wool Mark Test Method 31).
  • the present invention relates to the animal fiber which, with respect to a value represented by a difference ( ⁇ a - ⁇ w ) between the coefficient of friction in the tip to root direction ( ⁇ a ) and the coefficient of friction in the root to tip direction ( ⁇ w ) with respect to a fiber direction, measured in accordance with JIS L-1015 method, has a reduction of not less than 30 % in comparison with the difference ( ⁇ a - ⁇ w ) of untreated animal fiber in coefficient of static friction or in coefficient of dynamic friction, with the value of ⁇ a being approximately the same as a value in the case of the untreated animal fiber and the value of ⁇ w having an increase of not less than 30 % in comparison with a value in the case of the untreated animal fiber.
  • the present invention also relates to the animal fiber in which the pilling resistance is not lower than third class in JIS L-1076.6.1A method.
  • the present invention relates to the animal fiber wherein, supposing that an absorbance of an absorption band corresponding to amide I is set to 1 in a reflection FT-IR measuring method, the degree of oxidation of a -S-S- bond (cystine bond) in a epidermal cell of the animal fiber is represented by a relative absorbance of not less than 0.1 in an absorption band of -SO 3 H group (sulfonic acid group) and/or a relative absorbance of not less than 0.08 in an absorption band of -S-SO 3 Na group (Bunte salts).
  • the animal fiber of the present invention is obtainable by a method comprising:
  • the method comprises: a
  • the present invention relates to animal fiber superior in shrink proofing and pilling resistance properties obtained by any one of the methods described above.
  • the degree of oxidation of a -S-S- bond is represented by a relative absorbance of not less than 0.1 in an absorption band of -SO 3 H group (sulfonic acid group) and/or a relative absorbance of not less than 0.08 in an absorption band of -S-SO 3 Na group (Bunte salts)
  • the relative absorbance in an absorption band of -SO 3 H group (sulfonic acid group) more specifically refers to a relative absorbance of the absorption band of 1040 cm -1 corresponding to the -SO 3 H group (sulfonic acid group) measured by the reflection FT-IR measuring method (ATR method) in the case when the absorption band of 1650 cm -1 corresponding to amide I is set to 1.
  • the relative absorbance in an absorption band of -S-SO 3 Na group refers to a relative absorbance of the absorption band of 1024 cm -1 corresponding to the -S-SO 3 Na group (Bunte salts) measured by the reflection FT-IR measuring method (ATR method) in the case when the absorption band of 1650 cm -1 corresponding to amide I is set to 1.
  • the animal fiber of the present invention is characterized in that it has superior shrink proofing and pilling resistance while maintaining a water repellent property that animal fibers originally possess.
  • the shrink proofing of the animal fiber of the present invention is represented by using the felting shrinkage rate or the difference in coefficient of friction in single fiber as a measure.
  • the shrink-proofing of the animal fiber of the present invention is not more than 8 % in the area shrinkage rate in a three-hours aqueous washing. More preferably, it is not more than 5 %.
  • the felting shrinkage rate is measured in conformity with WM TM31 method (Wool Mark Test Method 31), and a fabric knitted into a cover-factor C.F. 0.41 with one thread being taken from 14 gages is used as a sample.
  • conformity to "WM TM31 method” refers to the fact that the measurements were carried out in accordance with the testing procedure of WM TM31 method set based upon the ISO 6330 method, while the test washing machine was changed to a Cubex shrinkage testing machine.
  • the coefficient of friction of the single fiber is measured in accordance with JIS L 1015, and the following conditions are used:
  • ⁇ a is a coefficient of friction in the tip to root direction with respect to a fiber direction
  • ⁇ w is a coefficient of friction in the root to tip direction with respect to a fiber direction
  • the pilling resistance of the animal fiber of the present invention is quantitatively represented by a pilling test method in accordance with JIS L 1076.6. 1A, and it is not lower than the third class in pilling resistance.
  • Water repellency is evaluated by putting a water droplet on a knitted fabric made of animal fibers to be tested and observing the permeability of the water droplet into the knitted fabric.
  • the criteria of the evaluation are:
  • the evaluation of water repellency may be made by putting a sample in the form of sliver on the surface of water and measuring the time at which the sliver absorbs water and sinks into water.
  • a water droplet stays after a lapse of 30 minutes in the same manner as natural animal fibers.
  • the superior properties of the animal fiber of the present invention is achieved by changing conformation of scale structure, and by exemplifying the surface structure of wool, the mechanism of exertion of such superior shrink proofing and pilling resistance that the inventors, etc., of the present invention have found is explained below.
  • Fig. 1 (quoted from Wool Science Review Vol. 63 (1986)) is a schematic longitudinal cross-sectional view that shows the surface portion of a wool fiber.
  • An epidermal tissue (cuticle) portion called scales, consists of an epicuticle layer (21), an exocuticle A-layer (22), an exocuticle B-layer (23) and an endocuticle layer (24) as an innermost layer that are stacked in this order from outside.
  • the outer surface of the epicuticle layer is combined with a layer having a thickness of approximately 0.9 nm that is made from a higher fatty acid (mainly made of eicosanoic acid) which is bonded to a -SH residue of a polypeptide chain in the epicuticle layer through a thioester bond, and the alkyl group of this eicosanoic acid allows the animal fiber to exert a superior water repellence property.
  • a higher fatty acid mainly made of eicosanoic acid
  • eicosanoic acid is connected with an epicuticle layer (cystine content: 12%) via a thioester bond, and further, the epicuticle layer and an exocuticle A layer (cystine content: 35%) adjacent to the lower side of the epicuticle layer form an integrated structure, occupying about 20% of the total thickness of the cuticle, and cystine bonds are distributed in this tissue concentrically in an amount of about 70% based on the whole cystine content of the cuticle. The remaining about 30% is known to be composed of an exocuticle B layer (cystine content: 15%) and an endocuticle (cystine content: 3%).
  • cuticle tissue is composed of an exocuticle A and B layers and endocuticle layer, and the exocuticle A layer form an integrated tissue structure with epicuticle layer, and the felting phenomenon depends, substantially, on the exocuticle B layer and endocuticle layer.
  • each layer absorbs water more or less and swells. But, naturally, the more cystine crosslinkage develops, the less the extent of swelling with water is. And therefore, when animal fiber is immersed in water, endocuticle layer having lower cystine crosslinked density which is the innermost layer, is swollen with water and extends, but on the contrary, the outer layer, exocuticle layer, having higher cystine crosslinked density has less extent of water swelling and therefore the extent of the expansion in the exocuticle layer is smaller. Such difference of the expansion by difference of swelling produces the edge of uprising of the scale and resulting the entanglement of fiber with fiber, causing felting.
  • fibers are entangled with each other, and onto the entangled portions, other fibers are entangled by an external force applied to the fabric at the time of aqueous washing so that the entire fibers are drawn in the entangled portions, causing shrinkage in the length of the entire fiber lump to form felt; thus, felting results in further shrinkage.
  • the animal fiber of the present invention which is superior in shrink proofing and pilling resistance is mainly realized by a chemical modification of the epidermal tissue, and the swelling properties of the exocuticle B-layer and the endocuticle layer are made virtually equal to each other with the water repellence property of the eicosanoic acid on the uppermost surface being maintained so that, even when dipped into water, the rising of the scales is virtually eliminated.
  • the above-mentioned structural change by the treatment of the present invention is confirmed by a reflection FT-IR measuring method (ATR method).
  • ATR method a reflection FT-IR measuring method
  • the structure within 1 ⁇ m from the surface is reflected by the reflection FT-IR measurements, and this is equivalent to the thickness of the epidermal tissue of the animal fiber that is approximately 1 ⁇ m.
  • the conventional shrink proofing animal fiber has a smoother scale surface so that in comparison with the animal fiber of the present invention which maintains the scales, there is a reduction in the single-fiber drawing abrasion resistance, failing to provide sufficient pilling resistance.
  • Fig. 2 shows the results of surface observation under an electronic microscope of the animal fiber of the present invention, the shrink proofing animal fiber treated by the conventional method and a natural untreated animal fiber.
  • Fig. 2 shows an untreated wool fiber
  • (b) shows a chlorine-treated wool fiber
  • (c) shows a Chlorine-Hercosett treated wool fiber
  • (d) shows a wool fiber of the present invention.
  • the animal fiber of the present invention maintains a surface state that is virtually the same as the natural state.
  • the animal fiber of the present invention includes wool, mohair, alpaca, cashmere, llama, vicuna, camel and angora.
  • the animal fiber being relatively less performance in pilling property which has the feature described above, can be produced by the method for preparation according to the present invention described below.
  • the method for preparation of animal fiber of the present invention comprises that sliver composed of animal fiber is, first, primary-oxidized with an oxidizer having an ability to oxidize a cystine -S-S-bond of the animal fiber, and then, an ozone-oxygen mixed gas is made into ultrafine bubbles of 5 ⁇ or less in water by using a line mixer and the gas in this condition is allowed to collide against the previously primary-oxidized animal fiber for a given time to cause a gas-phase oxidation reaction in the liquid, resulting in oxidation of the cystine bond of wool into higher order oxidized state. Then, a reduction treatment is performed on the higher order-oxidized animal fiber to cleave the cystine crosslinkage (-S-S-).:
  • the method of the present invention also has the feature can continuously impart the combined effect of shrink proofing and pilling resistance to the sliver of animal fiber.
  • the primary-oxidized state of a cystine bond namely, lower order oxidized state means mono-oxidized state (-SO-S-), di-oxidized state (-SO 2 -S-) or mixed state thereof. Particularly, it means the state rich in mono-oxidized state. While, the higher order oxidized state means di-oxidized state, tri-oxidized thereof.
  • the present invention is characteristic in that it effects two-stage oxidation comprising a first step in which animal fiber is subjected to primary oxidation treatment by pad steaming with an oxidizer having an ability to oxidize a cystine -S-S- bond of the animal fiber and a second step in which higher order oxidation is conducted by blowing aqueous treatment liquid containing ozone in the form of ultrafine bubbles of 5 ⁇ or less in the aqueous treatment liquid, for cleaving a cystine bond only in cuticle portions of animal fiber effectively, namely, in a short period of time without unevenness treatment.
  • a mixed gas of ozone and oxygen produced from an ozone generating apparatus is blown in a liquid circulation pump, further, aqueous ozone treatment liquid containing ozone in the form of ultrafine bubbles of 5 ⁇ or less is prepared through a line mixer, this liquid blown in water on animal fiber primary-oxidized, to ozone-oxidize quickly and preferentially an exocuticle B layer in which a cystine -S-S- bond has been previously oxidized to give higher order oxidized state in the B layer.
  • a cystine (-S-S-) bond is cleaved by reduction treatment with a reducing agent, for example, a sulfite, to lower the cystine crosslinked density of the exocuticle B layer, as a result, swelling, fluidization and solubilization with water are promoted and a part of protein is allowed to flow out of the fiber,
  • a reducing agent for example, a sulfite
  • the cystine crosslinked density of this exocuticle B layer is reduced by performing pre-oxidation, ozone oxidation and reduction treatment with a sulfite, and as a result of that, about the same level water swelling as that of the endocuticle is obtained and bilateral function of the exocuticle B layer and endocuticle is allowed to disappear. And therefore the edge of scale does not uprise even when animal fiber is immersed in water, and shrinkage does not occur in aqueous washing. Simultaneously, higher degree of shrink proofing is given without deteriorating water repellency since an epicuticle layer and a thioester of eicosanoic acid covering the surface thereof is still kept.
  • the method for preparation of the animal fiber of the present invention is characteristic in two-stage oxidation comprising a first step in which animal fiber is primary-oxidized and a second step in which the primary-oxidized animal fiber is higher order-oxidized, and in comprising a successive reduction step to cleave the higher order oxidized cystine bond.
  • the first step in this method is a pre-treatment step for oxidation of a cystine bond with ozone, and is a stage in which a cystine bond in cuticle tissue of the fiber is primary-oxidized with an oxidizer having an ability to oxidize a -S-S- bond of animal fiber to obtain substantially mono-oxidized state.
  • persulfuric acid, peracetic acid, performic acid, per-acids and neutral salts or acidic salts of these per-acids, or potassium permanganate, hydrogen peroxide and the like are exemplified, and these can be used alone or in admixture of two or more.
  • Particularly preferable oxidizer is potassium hydrogen persulfate.
  • the primary oxidation is conducted through pre-oxidation by a pad (impregnation)-steam (reaction) method, in some occasions, by pad-store (reaction at room temperature).
  • a pad impregnation
  • reaction steam
  • pad-store reaction at room temperature.
  • potassium hydrogen persulfate an immersion method is adopted, and in this case, a treating reagent permeates into inner portions of fiber and the fiber or whole fiber is oxidized and hydrolyzed to cleave a cystine bond, causing reduction in mechanical properties such as strength, elongation and the like. Nevertheless, shrink proofing effect is not obtained.
  • reaction with the fiber does not occur and cuticle is not oxidized sufficiently unless the reaction temperature is room temperature or more (substantially, 32°C).
  • the treatment condition should be set depending on the kind of an oxidizer used and reactivity thereof with the fiber, and in the case of use of potassium hydrogen persulfate, the pad (impregnation)-steam (reaction with heat) method oxidizes a cystine bond only in cuticle portions while preventing oxidation of inner portions of the fiber, thereby, makes easy the subsequent higher order oxidation of cuticle portions with ozone.
  • an exocuticle B layer is primarily oxidized at first (first step).
  • first step Comparing to exocuticle B layer, in the tissue of the epicuticle layer and exocticle A layer being in contact with it, cystine -S-S- crosslinked density is very high, and as a result, the tissue has very high hardness, and manifests chemical resistance and abrasion resistance (this epicuticle part is tissue decomposed lastly even by hydrolysis with 6N-hydrochloric acid. Therefore, epicuticle is treated as a resistant membrane in histology). According to this, exocuticle B layer is more susceptible to oxidation relatively in comparison with epicuticle layer and exocuticle A layer.
  • a wetting agent is put into a bath charged with an oxidizer aqueous solution, the bath temperature is controlled as lower as possible than room temperature, padding (impregnation) is effected so that liquid contact time with animal fiber will be several seconds (about 2 to 3 seconds), the fiber is removed out of the pad bath at a stage wherein the oxidizer aqueous solution does not reach inner portions of the fiber and sufficiently permeates into cuticle, and immediately, squeezed by a mangle so that add-on amount of the oxidizer aqueous solution becomes constant.
  • the fiber thus containing a given amount of the oxidizer aqueous solution is subsequently treated at temperatures around 95°C in steamer, for promoting a primary oxidation reaction while avoiding drying of the fiber.
  • the term "padding” does not mean impregnation of liquid into fiber by merely putting the fiber in a bath but means impregnation so as not to cause a reaction in the immersion bath in view of chemical reactivity of the oxidizer used with animal fiber. It means poor reaction conditions, namely, selection of a wetting agent having high permeability which is not decomposed with an oxidizer in a bath, control of the temperature in a bath as low as possible to suppress a reaction with fiber, and immersion for a short period of time such as several seconds and subsequent immediately squeezing.
  • the second step in the treatment method is a stage in which animal fiber primary-oxidized with an oxidizer is higher order-oxidized with ozone.
  • oxidation with ozone a longer period of time is required, and formation of oxidation state sufficient for cleaving of a cystine bond is difficult. That is, when animal fiber is oxidized with ozone, it is necessary to treat the animal fiber with an ozone gas or ozone dissolved in water of high concentration for 10 to 30 minutes, and under such conditions, continuous treatment was impossible.
  • the present invention is characteristic in that ozone is dispersed in the form of ultrafine bubbles of 5 ⁇ or less at high concentration in water, and further, this aqueous treatment liquid containing ozone in such state is blown to animal fiber, to cause a gas-solid reaction with gas phase of ozone.
  • a means for solving this drawback a means is adopted in which, first, top sliver of animal fiber is sufficiently fiber-opened by a rotary gill to form a thin web like belt, wound on the surface of a perforated suction drum, and an ozone-oxygen mixed gas is made into ultrafine bubbles of 5 ⁇ or less by using a line mixer, and the liquid is sucked to increase the number of collision against fiber for allowing this ultrafine bubbles to penetrate between fiber and fiber, thereby promoting ozone oxidation.
  • the animal fiber sliver used is, for example, a top of about 25 g/m, and the nine ends of tops are fiber-opened using a gill to form a belt, and the draft ratio is from about 1.4 to 4-fold, preferably 1.66-fold, though it varies depending on fineness of wool.
  • the feeding speed of a wool top is from 0.2 m/min to 4 m/min, preferably from 0.5 m/min to 2 m/min.
  • the wool top shaped in the form of a belt is immersed in an aqueous solution containing an oxidizer and wetting agent, and squeezed with a squeezing mangle.
  • the oxidizer include persulfuric acid, persulfates or acidic persulfates such as potassium hydrogen persulfate, sodium hydrogen persulfate, ammonium persulfate, potassium persulfate and sodium persulfate; potassium permanganate, hydrogen peroxide, performic acid or salts thereof, peracetic acid or salts thereof, and the like.
  • potassium hydrogen persulfate [trade name: "Oxone” (2KHSO 5 ⁇ KHSO 4 ⁇ K 2 SO 4 , active composition is 42.8% as the proportion of KHSO 5 ) ; manufactured by E. I. du Pont de Nemours and Company] since it is in the form of a granule, easily dissolved, and an aqueous solution containing the dissolved oxidizer is stable for storage at a temperature of 32°C or less.
  • the wetting agent "Alcopol 650" (manufactured by Chiba Specialty Chemicals K.K.) is preferable since it is stable against an oxidizer.
  • the concentration of the oxidizer is from 10 g/L to 50 g/L, preferably from 20 g/L to 40 g/L when the squeezing ratio is 100% in the case of potassium hydrogen persulfate "Oxone", though it differs depending on the kind of the oxidizer.
  • the concentration of the wetting agent is suitably about 2 g/L in the case of "Alcopol 650".
  • the temperature of the pad liquid is preferably as low as possible so as not to cause a reaction in the liquid. Particularly preferably, it is from 15°C to 25°C. It is preferable that pH of the liquid is on acidic side. More preferably, pH is 2.0.
  • an oxidizer is allowed to react with animal fiber sliver, and the treatment conditions vary depending on the kind of the oxidizer.
  • the treatment conditions vary depending on the kind of the oxidizer.
  • potassium permanganate, hydrogen peroxide, performic acid or peracetic acid a method in which an aqueous solution of these compounds is padded, and then, stored at room temperature is recommendable.
  • the store time may advantageously be about 2 to 10 minutes though it varies depending on the kind and concentration of the oxidizer.
  • a primary oxidation reaction may advantageously be conducted by steaming treatment at normal pressure, after padding of an aqueous solution of these compounds.
  • a temperature of 95°C and a time from 5 to 15 minutes, preferably of about 10 minutes are sufficient to conducting primary oxidation.
  • cystine (-S-S-) content varies depending on tissues constituting cuticle and cortex.
  • modification of cuticle tissue is conducted for imparting shrink proofing and pilling resistance .
  • Oxidation of a cystine bond -S-S- progresses sequentially as described below, and the -S-S- bond is cleaved after hydrolysis and reducing treatment, and finally, sulfonic acid (-SO 3 H) is obtained.
  • the present invention has a feature that a reaction is effected by a pad-steam method with an oxidizer, for example, potassium hydrogen persulfate, a -S-S- bond is stopped at substantially mono-oxidized state, and is further oxidized to higher order using ozone in the subsequent step.
  • an oxidizer for example, potassium hydrogen persulfate
  • the ozone oxidation reaction rate increases remarkably as compared with oxidation rate when ozone is solely used or potassium hydrogen persulfate is solely used, and continuous treatment of animal fiber sliver becomes possible for the first time, leading to success in industrialization, if a-S-S- bond is primary-oxidized previously, and then, ozone-oxidized, as shown in the following formula:
  • the present invention is characteristic in that an ozone-oxygen mixed gas is allowed to collide against animal fiber sliver by blowing the gas in the form of ultrafine bubbles of 5 ⁇ or less in water, to cause a higher order oxidation through a gas phase reaction.
  • an ozonizer apparatus manifesting a generating capacity of about 250 g/hr (for example, one manufactured by Chlorine Engineering K.K.) can sufficiently effect continuous treatment of animal fiber sliver, and for example, an ozone gas generated by feeding an oxygen gas at a rate of 40 L/min into the ozonizer has a weight concentration of 6.5 wt% and a volume concentration of 0.1 g/L in the mixed gas, and in one example, treatment with an ozone oxygen mixed gas of 4 g/min was an optimum condition though it differs depending on the extent of primary oxidation and other conditions.
  • the feeding amount for imparting shrink proofing and pilling resistance to wool fiber is 6%owf or less, preferably from 1.5%owf to 5%owf based on the weight of wool, though it differs depending on the wool fiber quality.
  • the ozone gas for reacting an ozone gas efficiently with wool, the ozone gas is formed into bubbles which are as fine as possible in water, the bubbles are allowed to collide against wool, and an oxidation is caused at the collision site. Therefore, also since the water solubility of ozone is extremely low, only cuticle tissue of wool is resultantly oxidized, and cortical tissue which is inner tissue is protected, resulting in further enhancement of the effect to modify the surface of wool.
  • a method for making an ozone-oxygen mixed gas into ultrafine bubbles of 5 ⁇ or less a method is preferable in which the mixed gas is introduced into a water flow pump and the mixed gas is allowed to collided against small walls in a cylinder by raising water pressure to give ultrafine bubbles.
  • a special apparatus shown in Fig. 4 was contrived for collecting ultrafine bubbles produced in a line mixer and blowing the bubbles on wool sliver in the form of a belt.
  • Wool sliver (2) in the form of a belt which has been primary-oxidized is sandwiched between stainless mesh belts (1) and (3) and transferred to an ozone treatment bowl (9) equipped with a suction drum (5), where the ultrafine bubbles are blown on wool sliver in the form of a belt through a nozzle (6) from a line mixer (13).
  • an ultrafine bubble-collecting apparatus (4) is mounted on the periphery of a suction drum, and further, liquid containing the ultrafine bubbles is sucked from the center portion (7) of the suction drum to allow the ultrafine bubbles to collide against the wool sliver in the form of a belt.
  • An ozone-oxygen mixed gas produced from an ozonizer (11) is introduced in a water suction pump (12) to cause gas-liquid mixing, and the mixture is fed to the line mixer (13) by raising water pressure to produce ultrafine bubbles which are blown on wool sliver in the form of a belt sandwiched between stainless mesh belts. Further, surface oxidation of wool fiber is completed by using an apparatus sucking through a suction port (7).
  • the ozone oxidation is conducted at the acidic side of pH 1.5 to pH 2.5, preferably, of pH 1.7 to pH 2.0.
  • Ozone has higher solubility, however, lower reactivity, in cold water.
  • the treatment temperature has to be increased for enhancing the reactivity, and the treatment temperature may advantageously be 30°C to 50°C, and when it is too high, an ozone-oxygen mixed gas shows higher molecular movement, and is scattered out of a treatment bowl. Particularly preferable temperature is 40°C.
  • the reaction time can control the reaction by the feeding speed of wool sliver, namely, the liquid contact time in the ozone treatment bowl. When the feeding speed of sliver is 0.5 m/min, the contact time is 2 minutes, and when 2 m/min, the contact time is 33 seconds, and control of shrink proofing and control of pilling resistance are possible by controlling the reaction time.
  • the wool sliver ozone-oxidized in the ozone treatment bowl is treated with a reducing agent, and therein, a -S-S-bond is cleaved for the first time as shown in the following formula.
  • the reducing agent is not particularly restricted, and sulfites are suitable.
  • sodium sulfite Na 2 SO 3 (pH 9.7) is more preferable than acidic sodium sulfite NaHSO 3 (pH 5.5). Since primary oxidation and ozone oxidation are conducted at the acidic side, reduction treatment at the alkaline side is preferable also from the standpoint of neutralization treatment.
  • the concentration of sodium sulfite is preferably from 10 g/L to 40 g/L, and particularly preferably around 20 g/L.
  • the temperature is preferably from 35°C to 45°C, and particularly preferably around 40°C.
  • the temperature may advantageously be about 40°C.
  • a softener and spinning oil agents may be added to the final bowl in view of hand-feeling and spinning property of wool sliver.
  • treatment can also be conducted at 40°C by adding 1 g/L of Alcamine CA New (manufactured by Chiba Specialty Chemicals K.K.) and 1 g/L of Croslube GCL (manufactured by CTC Textiles Ltd./Miki K.K.).
  • Drying is conducted preferably at relatively lower temperatures around 80°C in a suction type drier for avoiding heat yellowing.
  • the two-stage oxidation method used in the present invention enables unexpected effective oxidation which has not been obtained by oxidation treatment either with an oxidizer or ozone.
  • a cystine bond is cleaved uniformly by higher order oxidation of animal fiber and the followed reduction treatment, and resultantly, animal fiber endowed uniformly with shrink proofing and pilling resistance is obtained by continuous steps.
  • the exocuticle B layer is selectively attacked and the integrated structure of epicuticle and exocuticle A layers which is a structurally hard tissue is preserved, and resultantly, eicosanoic acid revealing water repellency is also kept and water repellency of the whole fiber, and fiber strength is also maintained.
  • a cystine (-S-S-) bond is oxidized and hydrolyzed to give sulfonic acid (-SO 3 H), and since a peptide chain constituting animal fiber is cleaved in addition to cleavage of a cystine bond, the tensile strength and elongation of fiber are lowered. Also thioester bond tissue formed between eicosanoic acid which is the outermost film of animal fiber and a -SH group in a polypeptide chain is broken, to convert the hydrophobicity into the hydrophilicity. Therefore, water repellent function inherent to wool disappears.
  • Wool sliver was treated continuously according to a process diagram described in Fig. 3.
  • the running speed of the sliver through processes namely, a pad treatment mangle, ozone treatment bowl, reducing treatment bowl, water rinsing treatment bowl and drying processes was 2 m/min.
  • Wool sliver wetted in the form of a belt was subjected to steam treatment on a conveyor net under the following conditions. 95°C, 10 min
  • the sliver was transferred to an ozone treatment bowl.
  • the steam-treated sliver was transferred to a suction type ozone treatment bowl, and ozone-oxidized under the following conditions.
  • Ozonizer (“OZAT CFS-3", manufactured by Chlorine Engineering K.K.) was used at 250 g/hr, and an oxygen bomb was used as an oxygen source.
  • the generated ozone gas was transferred to four line mixers through 4 pumps having a water lifting amount of 80 L/min.
  • the ozone blowing amount in each line mixer was 10 L/min, and the total amount was 40 L/min.
  • the ultrafine bubbles were allowed to collide against on the wool sliver on the suction drum by blowing the bubbles using an ultrafine bubble-scattering-preventing apparatus as shown in Fig. 4, and further, the treatment liquid was sucked from inside of the drum and was circulated to the outer side of the drum for increasing the times thereof, and ozone treatment was conducted under the following conditions.
  • the sliver was transported to a reducing bowl.
  • the ozone-treated sliver in the form of a belt was treated under the following conditions in a suction type reducing bowl.
  • the sliver was transported to a water rinsing bowl.
  • the reduction-treated sliver in the form of a belt was treated with hot water of 40°C for 33 seconds in a suction type water rinsing bowl. After the water rinsing, the sliver was further transported to another water rinsing treatment bowl.
  • the sliver in the form of a belt was treated with hot water of 40°C for 33 seconds in a suction type water rinsing treatment bowl. After the water rinsing, the sliver was transported to the final bowl for imparting a spinning oil and softener necessary for the subsequent processes.
  • the water-rinsed sliver in the form of a belt was treated with hot water of 40°C for 33 seconds in a suction type treatment bowl charged with the following treating agents.
  • the sliver was transported to a drier.
  • Drying was conducted at 80°C using a suction type hot air drier.
  • the treated sliver in the form of a belt was gilled and spun into hosiery yarn of 2/48Nm by twist of Z500 ⁇ S300, and strength and elongation of the yarn were measured, and knitted into a density of a cover factor C.F. of 0.41, and washed continuously for 1 hour and 3 hours by a Cubex shrinkage testing apparatus.
  • the fabric which had been knitted into a C.F. of 0.41 was subjected to a pilling test for 5 hours by an ICI pilling tester.
  • the surface of the wool was observed by an electron microscope, S-3500N manufactured by Hitachi.
  • the sliver was gilled to be fiber-opened, and each 1 g of the treated sliver and untreated sliver was sampled, 800 mL of distilled water was charged into a 1-L beaker and the sample was floated on the water surface and sedimentation condition was observed. The results thereof are shown in Table 1.
  • the treated wool sliver was soft and showed white color, and shrink proofing thereof based on WM TM31 method met the standard of area shrinkage percentage under the Wool Mark washability requirement, and also, satisfied 4-th grade level of pilling resistance in the ICI pilling test.
  • the observation of the sedimentation state of 1 g of the sample showed that both of the un-treated wool and the ozone-treated wool did not precipitate even after left for a day and night and were floating on water surface in the beaker, while, the wool treated by a chlorinated resin method (Chlorine Hercosett method) sank beneath water surface in the beaker only after left for 2 to 3 minutes.
  • shrink proofing can be imparted without losing water repellent function owned by natural wool.
  • a method in which chlorine-treated wool surface is coated with a Hercosett resin (polyamide epichlorohydrin) is mainly used. On the wool treated thereby, water repellent function tends to be lost and the wool tends to be wetted and resultantly, body temperature is lowered due to high heat conductivity of water, giving chilled feeling to wearer, though shrink proofing is obtained.
  • the surface of the treated wool was observed by using S-3500N low evacuated electron-microscope manufactured by Hitachi which can observe the object in wet condition showed that scale edge of the wool did not uprise, namely, differential frictional effect (D.F.E) was not found, and on the contrary, in the un-treated wool, scale of the wool uprose owing to swollen with water, which is a cause of felting. Therefore, the present invention is a shrink proofing method which does not uprise scale edge of wool in water.
  • a sliver of 20.7 ⁇ (25 g/m, 9 ends, draft ratio: 1.66-fold) of Merino wool from Australia was continuously treated according to the method in Example 1 using.
  • the ozone treatment using an ultrafine bubble-scatter-preventing apparatus was omitted.
  • the results thereof are shown in Table 1. Though the treated wool was bleached, shrink proofing and pilling resistance were approximately at the same level as those of the un-treated wool, and no treatment effect was appreciated.
  • Example 1 From comparison of Example 1 with Comparative Example 1, it became apparent that on wool which had been treated previously with potassium hydrogen persulfate as a pre-treatment process, oxidation progresses quickly with a small amount of ozone.
  • the present invention exemplified in Example 1 is an revolutionary method in which wool fiber can be modified to impart shrink proofing and pilling resistance with a small amount of ozone, and as the result, treatment effect is manifested sufficiently with a small capacity of ozonizer, and consequently, equipment investment decreases and exhaust gas treatment is reduced, and deterioration in working environment is prevented.
  • a sliver of 20.7 ⁇ (25 g/m, 9 ends, draft ratio: 1.66-fold) of Merino wool from Australia was continuously treated according to the method in Example 1 using. However, the pre-treatment using potassium hydrogen persulfate was omitted. The results thereof are shown in Table 1. Though the treated wool was somewhat bleached, shrink proofing and pilling resistance were completely at the same level as those of the un-treated wool.
  • the treated wool sliver was gilled and spun into hosiery yarn of 2/48Nm by twist of Z500 ⁇ S300, and knitted into a density of a cover factor C.F. of 0.41, and continuous washing tests for 1 hour and 3 hours by a Cubex shrinkage testing apparatus, and further, a pilling test for 5 hours using an ICI pilling tester were conducted, and strength and elongation of the knitted yarn were measured.
  • 1 g of the treated sliver was fiber-opened by a gill, 800 mL of distilled water was charged into a 1-L beaker and the sliver was floated on the water surface and sedimentation condition was observed.
  • the results of the tests are shown in Table 1.
  • the treated wool sliver was soft and also reveals whiteness, and further, by increasing the ozone feeding amount by about 3.6-fold of that in Example 1, shrink proofing was much superior to the Wool Mark washability requirement, and such high degree of pilling resistance that the result of an ICI pilling test was 5-th grade even after 5 hours was obtained. Since the reaction amount of ozone was increased, strength and elongation of the knitted yarn somewhat decreased, and regarding water repellent resistance, in the case of chlorine-treated wool, completion precipitation to beneath water surface was observed, and this treated wool revealed slight reduction as compared with natural non-treated wool.
  • Example 2 The same processes as Example 1 were carried out except that the contact time of the ozone treatment was set to one minute so that a shrink proofing treatment was carried out on Merino wool of 20.7 micron from Australia.
  • the resulting shrink proofing wool fiber was evaluated on its properties, and the results are listed in Table 2 in comparison with untreated wool, chlorine treated wood and Chlorine-Hercosett treated wool.
  • electronic microscopic photographs of the fiber surface are shown in Fig. 1, and the results of water repellency tests using a water droplet dripping method onto a knitting fabric are shown in Fig. 5.
  • the felting shrinkage rate was measured in conformity with WM TM31 method and the fabric knitted into a cover-factor C.F. 0.41 with one line being taken from 14 gages was used as a sample.
  • the pilling resistance was measured by a pilling test method in accordance with JIS L 1076.6. 1A by using the fabric knitted by IP18G.
  • the coefficient of friction ⁇ a in the tip to root direction to the scale direction of the single fiber and the coefficient of friction ⁇ w in the root to tip direction to a fiber direction were measured in conformity with JIS L 1015 under the conditions of a hanging line load of 200 mg and a cylinder peripheral velocity of 90 cm/min.
  • the fiber itself was measured by a reflection method (ATR method).
  • the figures are given as relative absorbances of the absorption bands corresponding to the -SO 3 H group and the -S-SO 3 Na group in the case when the absorbance of the absorption band corresponding to amide I is set to 1.
  • Table 2 shows the results of evaluation on the dying property by the use of a basic dye that provides a measure for the existence of sulfonic acid groups.
  • the shrink proofing wool fiber of the present invention allows scales to remain in the same degree as the natural untreated wool (Fig. 1), thereby maintaining a better water repellence property (Fig. 5).
  • pilling resistance is remarkably improved as compared with those conventional treated fibers that have only little improvements.
  • the felting shrinkage rate is greatly improved, and the difference in the coefficients of friction (static friction and dynamic friction) of the single fiber, which provides one measure for the felting shrinkage rate, that is, the difference " ⁇ a - ⁇ w " between the coefficients of friction in the tip to root direction and in the root to tip direction with respect to a fiber direction, becomes smaller, thereby making the anisotropy smaller.
  • the FT-IR data shows that, in comparison with the other fibers, the shrink proofing improved fiber of the present invention has much more sulfonic acid groups (-SO 3 H) and Bunte salts (-S-SO 3 Na), which indicate a higher order oxidized state, generated on the surface thereof, thereby indicating that the surface oxidation has been carried out efficiently.
  • Wool sliver was successively dipped in a chlorine treatment bath, and this was squeezed by a squeezing roll, and then dipped in an anti-chlorine treatment bath, and this was squeezed by a squeezing roll, washed with water, and then dried.
  • Chlorine treatment Chlorine gas was blown into water so as to set an amount of active chlorine in the range of 1.8 % to 2.0 % owf with respect to the weight of wool, and the treatment was performed at pH 2.0 in cold water for several tens of seconds.
  • Anti-chlorine treatment Sodium sulfite (40 g/L) was adjusted to pH 0.9 by using sodium bicarbonate, and the treatment was performed at 30°C for several tens of seconds.
  • Washing treatment The resulting fibers were dipped in a washing bath at 40°C for several tens of seconds, and then squeezed by a squeezing roll.
  • Drying treatment The resulting fibers were dried by using a suction-type drier.
  • the resulting wool sliver was dipped in a processing bath in which Hercosett resin WT-570 (made by Dick Hercules Co., Ltd.) had been dissolved, and this was squeezed, and then dipped in a treatment bath containing a softening agent and a spinning oil, squeezed, and then dried.
  • Hercosett resin WT-570 made by Dick Hercules Co., Ltd.
  • Hercosett resin treatment The resin bath concentration was set to 2 owf with respect to the weight of wool, the bath pH being adjusted to pH 7.5 with sodium bicarbonate, and the treatment was performed at 35°C for several tens of seconds, and the resulting wool was squeezed by a squeezing roll.
  • Softening treatment The bath temperature was adjusted so that Alcamine CA-New (made by Chiba Specialty Chemicals K.K.) serving as a softening agent was set to 0.5 % owf with respect to the weight of wool and Croslube GCL (made by CTC Textiles Ltd./Miki K.K.) serving as a spinning oil was set to 1.35 % owf with respect to the weight of wool, and the treatment was performed at 30°C for several tens of seconds, and the resulting wool was squeezed by a squeezing roll.
  • Alcamine CA-New made by Chiba Specialty Chemicals K.K.
  • Croslube GCL made by CTC Textiles Ltd./Miki K.K.
  • the present invention makes it possible to provide an animal fiber having superior shrink proofing and pilling resistance without impairing a water repellent property that animal fibers originally possess as a superior feature, as well as without causing degradation in the fiber mechanical properties. Moreover, the present invention also provides a manufacturing method of the animal fiber having the above-mentioned features, without using a toxic chemical such as chlorine, etc. In addition, the method used in the present invention makes it possible to carry out a continuous processes, and consequently to provide a useful method from the industrial point of view.

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  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (8)

  1. Fibre animale ;
       ayant des écailles de formes originales sur la partie superficielle de la fibre et étant oxydée à un degré d'oxydation d'une liaison -S-S- dans une cellule épidermique de la fibre animale non inférieur à 0,1 d'absorbance relative dans une bande d'absorption du groupe -SO3H et non inférieur à 0,08 d'absorbance relative dans une bande d'absorption du groupe -S-SO3Na (sels de Bunte) avec une absorbance d'une bande d'absorption correspondant à l'amide I réglée à 1 dans un procédé de mesure de réflexion FT-IR,
       présentant une résistance au rétrécissement d'un taux de perte de surface non supérieur à 8 % pendant un lavage aqueux de trois heures lorsqu'il est mesuré en tant que taux de rétrécissement par feutrage conformément au procédé de test 31 de Wool Mark et une résistance au boulochage non inférieure à la classe trois du procédé JIS-L-1076.6.1A, outre la propriété d'imperméabilité que la fibre animale possède à l'origine,
       ladite fibre pouvant être obtenue par un procédé qui comprend :
    a) une première étape dans laquelle une liaison -S-S- d'une cellule de cuticule d'une fibre animale est traitée par oxydation primaire en un état oxydé inférieur,
    b) une deuxième étape dans laquelle la liaison -S-S- primaire oxydée est traitée par oxydation en un ou plusieurs états oxydés d'ordre supérieur d'état di, tri ou tétra oxydé, et
    c) une troisième étape dans laquelle ladite liaison -S-S- dans un état oxydé supérieur est traitée par clivage de réduction.
  2. Fibre animale selon la revendication 1, dans laquelle, en tant que mesure de la résistance au rétrécissement, la valeur représentée par une différence (µa-µw) entre le coefficient de friction dans le sens de la pointe vers la racine (µa) et le coefficient de friction dans le sens de la racine vers la pointe (µw) par rapport à un sens de fibre, mesurée selon le procédé JIS L-1015, est réduite de 30 % ou plus en comparaison avec la différence (µa-µw) d'une fibre animale non traitée de coefficient de friction statique ou de coefficient de friction dynamique, la valeur de µa étant approximativement identique à une valeur dans le cas de la fibre animale non traitée, et la valeur de µw étant supérieure de 30 % ou plus en comparaison avec une valeur dans le cas de la fibre animale non traitée.
  3. Fibre animale selon la revendication 1 ou 2, dans laquelle la fibre animale est choisie dans le groupe constitué par la laine, le mohair, l'alpaga, le cachemire, le lama, la vigogne, le chameau et l'angora.
  4. Fibre animale selon la revendication 1, dans laquelle,
       dans la première étape (a) une liaison -S-S- dans une cellule de cuticule d'une fibre animale est traitée par oxydation primaire avec un oxydant ayant la capacité d'oxyder une liaison -S-S- cystéine dans une fibre animale, et
       dans la seconde étape (b) la liaison -S-S- primaire oxydée est traitée par oxydation à l'ozone.
  5. Fibre animale selon la revendication 4, dans laquelle l'oxydant est un ou un mélange de deux composés ou plus choisis dans le groupe constitué par l'acide persulfurique, l'acide peracétique, l'acide performique, les sels neutres et les sels acides de ces peracides, le permanganate de potassium et le peroxyde d'hydrogène.
  6. Fibre animale selon la revendication 4 ou 5, dans laquelle la première étape est conduite par un procédé foulard-vapeur de fibre animale en solution aqueuse d'agents oxydants.
  7. Fibre animale selon la revendication 4, dans laquelle le traitement d'oxydation à l'ozone est conduit par soufflage de liquide traitant à l'ozone aqueux contenant de l'ozone sous forme de bulles ultrafines de 5 µ ou moins sur la fibre animale dans ce liquide traitant à l'ozone.
  8. Fibre animale selon la revendication 4, dans laquelle la fibre animale est utilisée comme vêtement ou ruban composé principalement de fibres animales.
EP20010117262 2000-07-26 2001-07-17 Fibres animales non-rétrécissantes Expired - Lifetime EP1176245B1 (fr)

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US20080282478A1 (en) * 2005-08-10 2008-11-20 David Malcolm Lewis Improvements in and Relating to Wool Treatment
KR101253690B1 (ko) * 2009-09-11 2013-04-15 구라시키 보세키 가부시키가이샤 개질된 수모 섬유의 제조 방법
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US3457213A (en) * 1967-05-04 1969-07-22 Du Pont Coapplication of softeners with an acid halide containing polymeric shrinkproofing agent to textile fibers
US4189303A (en) * 1978-05-10 1980-02-19 The United States Of America As Represented By The Secretary Of Agriculture Method of shrinkproofing animal fibers with ozone
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