EP0681053B1 - Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication - Google Patents

Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication Download PDF

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Publication number
EP0681053B1
EP0681053B1 EP19940303133 EP94303133A EP0681053B1 EP 0681053 B1 EP0681053 B1 EP 0681053B1 EP 19940303133 EP19940303133 EP 19940303133 EP 94303133 A EP94303133 A EP 94303133A EP 0681053 B1 EP0681053 B1 EP 0681053B1
Authority
EP
European Patent Office
Prior art keywords
fiber
graft
weight
ferrous
comonomer
Prior art date
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.)
Expired - Lifetime
Application number
EP19940303133
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German (de)
English (en)
Other versions
EP0681053A1 (fr
Inventor
Reizo Gomibuchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Sanmo Dyeing Co Ltd
Original Assignee
Nihon Sanmo Dyeing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nihon Sanmo Dyeing Co Ltd filed Critical Nihon Sanmo Dyeing Co Ltd
Priority to EP19940303133 priority Critical patent/EP0681053B1/fr
Priority to DE69428980T priority patent/DE69428980D1/de
Publication of EP0681053A1 publication Critical patent/EP0681053A1/fr
Application granted granted Critical
Publication of EP0681053B1 publication Critical patent/EP0681053B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/10—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof

Definitions

  • This invention relates generally to a fiber modified with carboxyl groups and, more specifically, to an acrylonitrile fiber to which methacrylic acid or a hydroxyalkyl methacrylate is graft-copolymerized.
  • the present invention is also directed to a process for producing such a modified fiber.
  • An acrylonitrile fiber has properties similar to wool but has a defect that its moisture or damp absorbing power is poor. No effective method is however known to impart hydrophilicity to the acrylonitrile fiber.
  • a method is known in which a vinyl monomer having an acidic group is graft-copolymerized to a polyester or polyamide fiber using an organic peroxide such as benzoyl peroxide.
  • EP-A-0262405 discloses a process for preparing a water absorptive composite material in which an aqueous solution of a polymerizable monomer comprising acrylic acid (at least partly in the form of alkali metal or ammonium salts) is applied to a prefabricated fibrous substrate, polymerized in situ and then crosslinked by the addition of a crosslinking agent to the composite.
  • the polymerizable monomer may also contain up to 20 mol % of optional comonomers and methacrylic acid, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are mentioned in that connection.
  • the substrate material is preferably a cellulose or polyester fiber but may also be polyacrylonitrile.
  • a modified fiber comprising an acrylonitrile-series substrate fiber and a graft comonomer graft-copolymerized to said substrate fiber in an amount of 3-60% by weight based on the weight of said substrate fiber, said graft comonomer being at least one member selected from methacrylic acid and hydroxyalkyl methacrylate.
  • the present invention provides a process for the production of a modified fiber, comprising graft-copolymerizing a graft comonomer to an acrylonitrile-series substrate fiber in an aqueous medium containing hydrogen peroxide and a source of ferrous ion, said graft comonomer being at least one member selected from methacrylic acid and hydroxyalkyl methacrylates.
  • the acrylonitrile fiber used in the present invention may be in any desired form such as a yarn, a cotton, a woven or non-woven fabric, a filament or a tow. If desired, the substrate fiber may be used in combination with another fiber.
  • the term "acrylonitrile-series fiber" used in the present specification and claims is intended to refer to a fiber formed of a homopolymer acrylonitrile or a copolymer of acrylonitrile with a vinyl comonomer.
  • the vinyl comonomers include methyl acrylate, vinyl acetate, acrylic acid, methacrylic acid, vinyl chloride, vinylidene chloride, methylvinylpyridine, styrenesulfonic acid and mixtures thereof.
  • the copolymer of acrylonitrile with the vinyl comonomer generally has a content of the acrylonitrile of at least 20% by weight, preferably 35-90% by weight.
  • the substrate fiber is graft-copolymerized and linked a graft comonomer in an amount of 3-60% by weight based on the weight of the substrate fiber.
  • the graft comonomer is selected from acrylic acid and hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
  • the graft comonomer is preferably copolymerized in an amount of 5-40% by weight.
  • the modified fiber according to the present invention may be prepared by graft-copolymerizing the graft comonomer to the substrate fiber in an aqueous medium containing hydrogen peroxide and a source of ferrous ion.
  • the ferrous ions source is preferably a ferrous salt such as ferrous sulfate, ferrous chloride, ammonium ferrous sulfate or ferrous nitrate.
  • the ferrous in salt is preferably present in the aqueous medium in an amount providing a ferrous ion concentration of 0.5 to 5 mmol/liter, more preferably 0.7 to 1.6 mmol/liter.
  • the concentration of the hydrogen peroxide in the aqueous medium is preferably 0.01 to 0.1 mol/liter, more preferably 0.01 to 0.06 mol/liter.
  • the hydrogen peroxide and the ferrous ion source together serve to accelerate the graft copolymerization.
  • the aqueous medium may contain an acid in an amount of 2 to 4 mmol/liter, preferably 2.5 to 3.5 mmol/liter, if desired.
  • the acid serves to enhance the grafting rate of the graft comonomer.
  • suitable acids include sulfuric acid, hydrochloric acid, phosphoric acid and formic acid.
  • the aqueous medium may further contain a sequestering agent such as EDTA, NTA or a phosphoric acid-type or sulfonic acid-type agent.
  • the graft comonomer is generally used in an amount of 5-100 parts by weight, preferably 10-60 parts by weight, per 100 parts by weight of the substrate fiber and wherein the weight ratio of said aqueous medium to said substrate fiber is generally 5:1 to 50:1, preferably 5:1 to 15:1.
  • the graft copolymerization is generally performed at a temperature and for a period of time so that the graft monomer is grafted to the substrate fiber in an amount of 3-60% by weight based on the weight of the substrate fiber.
  • the graft degree (weight percentage of the grafted comonomer based on the weight of the substrate fiber) is 5-40% by weight when a methacrylonitrile-series fiber is used as the substrate fiber.
  • the graft copolymerization is generally performed at a temperature of 40°-110°C for 30-240 minutes, preferably at 70°-110°C for 30-180 minutes, more preferably 90°-100° for 60-90 minutes.
  • the carboxy groups (-COOH) introduced into the substrate fiber by graft copolymerization of the graft comonomer may be converted into -COOM (M represents a cation) by reaction with a salt-forming cation.
  • the cation may be, for example, sodium ion, calcium ion, ferrous ion, cupric ion, zinc ion, manganese ion, silver ion, quaternary ammonium ion or quaternary organic amine ion.
  • the process according to the present invention uses a ferrous salt in a very small amount. Therefore, the modified fibers are not discolored and no specific step for the removal of the ferrous salt is required. Further, the reaction conditions for the modification treatment may be easily controlled so that the graft copolymerization can be homogeneously performed.
  • the modified fibers of the present invention have improved hydrophilicity and serve to function as a good adsorbent not only for basic, bad odor substances such as ammonia and amines, but also for metal ions.
  • Example 3 was repeated in the same manner as described except that modacrylic fibers (Kanebo Acryl VE1 manufactured by Kanebo Co., Ltd.) was substituted for Toraylon.
  • the modified acrylic fibers thus obtained had a graft degree of 8.1 %.
  • Example 1 was repeated in the same manner as described except that 2-hydroxyethyl methacrylate was substituted for methacrylic acid.
  • the modified acrylic fibers thus obtained had a graft degree of 9.3 %.
  • aqueous solution 100 ml containing 0.5 % of hydrogen peroxide, 0.02 % of ferrous sulfate, 1.5 % of methacrylic acid, 1.5 % of 2-hydroxyethyl methacrylate, 0.05 % a sequestering agent (Chelest NTB) and 0.1 % of sulfuric acid (50°Be), 10 g of acrylic yarn (Silpalon 100d/-48f, manufactured by Mitsubishi Rayon Co., Ltd.) were immersed. The mixture was gradually heated from room temperature to 100°C and maintained at that temperature for 1 hour. The treated fibers were washed well with water and dried to obtain modified acrylic yarn weighing 114 % of the raw mterial yarn. The analysis of the carboxylic group revealed that the modified yarn had a grafted methacrylic acid monomber content of 6.4 %.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (11)

  1. Fibre modifiée, comprenant une fibre de substrat de la série de l'acrylonitrile et un comonomère greffé copolymérisé par greffage à ladite fibre de substrat en une quantité de 3 à 60% en poids sur la base du poids de ladite fibre de substrat, ledit comonomère greffé étant au moins un membre sélectionné parmi l'acide méthacrylique et le méthacrylate d'hydroxyalkyle.
  2. Fibre modifiée selon la revendication 1, dans laquelle ladite fibre de la série de l'acrylonitrile est une fibre formée par un homopolymère d'acrylonitrile ou par un copolymère d'acrylonitrile avec un comonomère vinylique.
  3. Fibre modifiée selon la revendication 2, dans laquelle ledit comonomère vinylique est sélectionné parmi l'acrylate de méthyle, l'acétate de vinyle, l'acide acrylique, l'acide méthacrylique, le chlorure de vinyle, le chlorure de vinylidène, la méthylvinylpyridine et l'acide styrènesulfonique.
  4. Fibre modifiée selon la revendication 2 ou la revendication 3, dans laquelle ledit copolymère a une teneur en acrylonitrile d'au moins 20% en poids.
  5. Fibre modifiée selon l'une quelconque des revendications précédentes, dans laquelle ledit méthacrylate d'hydroxyalkyle est le méthacrylate de 2-hydroxyéthyle ou le méthacrylate de 2-hydroxypropyle.
  6. Procédé de production d'une fibre modifiée telle que définie dans la revendication 1, comprenant la copolymérisation par greffage d'un comonomère de greffage à une fibre de substrat de la série de l'acrylonitrile dans un milieu aqueux contenant du peroxyde d'hydrogène et une source d'ions ferreux, ledit comonomère de greffage étant au moins un membre sélectionné parmi l'acide méthacrylique et les méthacrylates d'hydroxyalkyle.
  7. Procédé selon la revendication 6, dans lequel ladite source d'ions ferreux est un sel ferreux.
  8. Procédé selon la revendication 7, dans lequel ledit sel ferreux est sélectionné parmi le sulfate ferreux, le chlorure ferreux, le sulfate d'ammonium ferreux et le nitrate ferreux.
  9. Procédé selon la revendication 7 ou la revendication 8, dans lequel ledit sel ferreux et ledit peroxyde d'hydrogène sont présents dans ledit milieu aqueux en des quantités de 0,5 à 5 mmol/litre et de 0,01 à 0,1 mol/litre, respectivement.
  10. Procédé selon l'une quelconque des revendications 6 à 9, dans lequel ledit comonomère de greffage est utilisé en une quantité de 5 à 100 parties en poids par 100 parties en poids de ladite fibre de substrat, et dans lequel le rapport pondéral dudit milieu aqueux à ladite fibre de substrat est de 5:1 à 50:1.
  11. Procédé selon l'une quelconque des revendications 6 à 10, dans lequel ladite copolymérisation de greffage est réalisée à une température de 40° à 110°C pour une période de temps telle que ledit monomère de greffage est greffé sur ladite fibre de substrat en une quantité de 3 à 60% en poids sur la base du poids de ladite fibre de substrat.
EP19940303133 1994-04-29 1994-04-29 Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication Expired - Lifetime EP0681053B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19940303133 EP0681053B1 (fr) 1994-04-29 1994-04-29 Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication
DE69428980T DE69428980D1 (de) 1994-04-29 1994-04-29 Carboxygruppenmodifizierte Cellulose- oder Acrylfasern und Verfahren zur Herstellung derselben

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19940303133 EP0681053B1 (fr) 1994-04-29 1994-04-29 Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication

Publications (2)

Publication Number Publication Date
EP0681053A1 EP0681053A1 (fr) 1995-11-08
EP0681053B1 true EP0681053B1 (fr) 2001-11-07

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EP19940303133 Expired - Lifetime EP0681053B1 (fr) 1994-04-29 1994-04-29 Fibres acryliques ou cellulosiques modifiées par des groupements carboxyl et procédé pour leur fabrication

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DE (1) DE69428980D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2366568A (en) * 2000-09-01 2002-03-13 Unilever Plc Method of treating fabric
WO2023190608A1 (fr) * 2022-03-31 2023-10-05 株式会社カネカ Résine modacrylique thermoplastique et composition de résine modacrylique thermoplastique la contenant

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT361888B (de) * 1977-03-21 1981-04-10 Chemiefaser Lenzing Ag Nassvernetzte faser auf cellulosebasis und ver- fahren zu deren herstellung
AT354972B (de) * 1977-04-14 1980-02-11 Chemiefaser Lenzing Ag Pfropfpolymerisierte hydroxylgruppenhaeltige polymerfasern
US4743267A (en) * 1982-06-21 1988-05-10 International Yarn Corporation Of Tennessee Process for improving polymer fiber properties and fibers produced thereby
JPS61166809A (ja) * 1985-01-19 1986-07-28 Hayashikane Zosen Kk 高吸水性樹脂粉粒体の製造方法
JPH0780970B2 (ja) * 1986-08-29 1995-08-30 三菱化学株式会社 吸水性複合材料の製造法
JP3239146B2 (ja) * 1992-11-10 2001-12-17 日本蚕毛染色株式会社 改質セルロース繊維及びその製造方法

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EP0681053A1 (fr) 1995-11-08
DE69428980D1 (de) 2001-12-13

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