Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P7/00—Dyeing or printing processes combined with mechanical treatment
  • D06P7/005—Dyeing combined with texturising or drawing treatments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/18—Homopolymers or copolymers of nitriles
  • C08L33/20—Homopolymers or copolymers of acrylonitrile
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/923—Ethylenic monomers containing at least one salt group
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer

Definitions

• This invention relates to bi-component textile fibres from acrylonitrile polymers and to a method for the production of bi-component fibres having a reversible crimp and advantageous dyeing properties.
• two suitable spinning solutions or melts can be spun using suitable apparatus to form two-component filaments in which the two components lie adjacent one another in the cross-section of the filaments. It is also known that filaments of this kind can develop a permanent, three-dimensional crimp providing the two components are shrinkable to different extents.
• two-component filaments can be produced from acrylonitrile polymers, the crimp of which is three-dimensional and varies under the influence of a swelling agent, for example water, returning to its original condition following removal of the swelling agent.
• a crimp of this kind is known as a reversible crimp.
• Reversibility is obtained by virtue of the fact that the two components which lie adjacent one another in the filament diifer in their capacity to absorb swelling agents, in particular water.
• the difference in their hydrophilic properties can be brought about by a difference in the ionisable group content.
• acrylonitrile copolymers with sulphobetaines to produce two-component fibres with a reversible crimp.
• the reversible-crimp bi-component fibres produced from acrylonitrile polymers usually contain a polymeric component with a large number of ionisable groups of acid or basic character, strongly acid groups such as sulpho groups, for example, being preferred.
• basic dyes for example the hydrogen or alkali metal ions in the sulpho groups of the polymer are exchanged for the donor cation of the dye. All the hydrogen or alkali metal ions are exchanged for dye ions providing firstly that a sufliciently long dyeing time is used and, secondly, that sufficient dye is used.
• copolymers of acrylonitrile and sulphobetaines as one of the component fila ments in the production of reversible-crimp fibres.
• the sulphobetaines used as comonomers are neutral and do not have any afiinity for dyes. For this reason, it is either impossible or takes an excessively long time to dye fibres containing polymers of this kind as one of their components dark or deep shades.
• filaments produced from such polymers are hydrophilic to a limited extent only and hence only show a limited reversibility of crimp, particularly when they are exposed to the high temperatures, normally used in the production of fibres.
• the polymers for example vinylpyridine-sulphobetaine, show a marked tendency to go yellow.
• a further object of this invention is a method of producing bi-component fibres having a reversible-crimp and which do not suffer from the aforementioned disadvantages as regards dyeing by spinning together a polymer of acrylonitrile as the first component, and, as the second component, a copolymer of acrylonitrile and copolymerisable, unsaturated hydrazido betaines compounds corresponding to the following general formula RI x- -nn-z r a-soswherein X is A or ANH or .A-NH-C H and A represents an aliphatic aromatic ,or araliphatic radical with an unsaturated copolymerisable group, R represents an alkylene radical, R and R" represent lower alkyl radicals or, together with N, represent a heterocyclic radical, stretching the resulting bi-component filament and heat-setting the filaments, fibres or the formed woven 3 or knitted fabrics.
• the heatsetting may be effected at temperatures of between
• suitable aftertreatment leaves two component fibres produced with these comonomers as one of the components, with a threedimensional reversible crimp in the sense that the crimp changes under the action of a swelling agent, for example water and returns to its original condition follownig removal of the swelling agent.
• a swelling agent for example water and returns to its original condition follownig removal of the swelling agent.
• the polymers may contain between 1 and 20%, preferably between 5 and 10%, of the aforementioned comonomers.
• Copolymerisation can be carried out by known processes using radical-forming catalysts, preferably with the persulphate/bisulphite Redox system in aqueous medium. Additionally, other copolymerisable unsaturated compounds may be combined with the hydrazido betaine monomers, such as acrylic acid esters, methacrylic acid esters and vinyl compounds.
• the relative viscosity of the co-polymers [1 1, as measured at 20 C. in dimethyl formamide at a concentration of 0.5 g./ ml., can with advantage be between 1.7 and 2.7.
• the other polymer used in the preparation of the twocomponent filaments is with advantage a homopolymer of acrylonitrile. It can be prepared by known processes, for example by precipitation polymerisation in aqueous medium using Redox catalyst systems. In place of a homopolymer, it is also possible to use a copolymer of acrylonitrile with 1 to of comonomer which does not contain any ionisable groups such as, for example, methyl acrylate, methyl methacrylate or vinyl acetate.
• the relative viscosity a of these polymers can with advantage be between 1.7 and 2.7.
• the two polymers are dissolved separately.
• suitable solvents include the solvents normally used for polyacrylonitrile, for example dimethyl formamide, dimethyl acetamide or dimethyl sulphoxide.
• the two solutions are spun together by the conventional processes used to produce two-component filaments.
• One'method of testing the components, after they have been combined to form a two-component filament, for their ability to develop a crimp following suitable after treatment is to measure the extent to which filaments which were subjected to the same after-treatment as single-component filaments, shrink on boiling. A difference in the shrinkage on boiling shows that a twocomponent filament made up of the two components is able to develop a crimp following suitable after treatment.
• One method of testing the components for their ability to develop a reversible crimp after they have been combined to form a two-component filament is to measure the longitudinal swelling of the single-component filaments. A difference in longitudinal swelling of approximately 0.4% or more between the two single component filaments indicates that the crimp of the two-component fibres will become reversible. Finally, the reversibility of the two-component fibres can be directly measured.
• the length of a fibre or of a small group or band of fibres is measured with a cathetometer under a small load (0.2 g./l80 den.).
• the fibre or the band of fibres is then boiled in water for 30 minutes free from any strain, dried at 70 C. over a drying agent and its length re-measured.
• the shrinkage on boiling is calculated from the initial length I and the final length in percent, as
• LA LE LA LE LE LE
• K The number of crimping curls in the fibre when it is dry (K is then determined by counting.
• the fibre held free from strain between the two grips is then kept for 6 hours in water heated to 70 C. in a separate vessel and the number of crimping curls in the fibre thus swollen (K The dry-wet cycle is repeated until reproducible values are obtained.
• KT-Kg The reversibility of crimp is calculated in percent as 100 (KT-Kg) KT EXAMPLE 1
• a copolymer of acrylonitrile containing 5% by weight of a carboxylic acid hydrazide sulphobetaine corresponding to the formula with an 1 value of 2.17 is converted with dimethyl formamide into a 23% by weight solution and spun by a conventional dry spinning process into single-component filaments with an individual denier of 9.6 (filaments A).
• a homopolymer of acrylonitrile with an 1 value of 2.17 is converted with dimethyl formamide into a 23% solution and spun by the same method into single component filaments with an individual denier of 9.6 (filaments B).
• the filaments are each stretched in a ratio of 1:4 in water heated to 98 C. and then wound on to a bobbin. Some of the filaments are dried for one hour at 70 C. under tension, and the other heated under tension for 15 minutes at C. The shrinkage on boiling and reversible longitudinal swelling of the filaments is then measured:
• the dyed and dried filaments A are dissolved in dimethyl formamide to which 1% cone. sulphuric acid has been added (25 mg. of fibres in 200 ml.) and the extinction values of the dyed solutions measured at 625 m Extinction of filaments A 7 EXAMPLE 2
• the solutions of Example 1 are spun by a conventional dry-spinning process into two-component filaments with an individual denier of 9.6.
• the filaments are stretched in water heated to 98 C. in a ratio of 1:4, and then airdried in a drying zone heated to 130 C.
• the filaments are then compression crimped and chopped into fibres. A sample of the fibres is boiled for 30 minutes in water and the reversibility of the crimp measured. It amounts to 38.0%.
• EXAMPLE 3 A copolymer of acrylonitrile containing 8% of a carboxylic acid hydrazide sulphobetaine corresponding to the with an 1;,,; value of 2.63, is made up into a 22% solution with dimethyl formamide and spun by a conventional dryspinning process into single-component filaments with an individual denier of 9.6. The filaments are stretched in water heated to 98 C. in a ratio of 1:4, dried under tension at 130 C. in a rotary dryer, crimped in a compression crimper, chopped into staple fibres and treated with steam at 116 C. One sample of each fibre is dyed at different pH-values by the standard process of Example 1. The pH-dependent dye absorption is clearly apparent. The extinction values of the dyed and dried fibres are measured as in Example 1:
• the filaments are stretched in water heated to 98 C. in a ratio of 1:4, shrunk by 20% in a drying zone heated to 130 C. and then dried.
• the filaments are compression crimped and chopped into staple fibres.
• a sample is boiled for 30 minutes in water and the reversiblllty of 1ts crunp measured.
• EXAMPLE 6 A copolymer of acrylonitrile containing 5% by weight of acrylic acid methylester and 8% by weight of an oxalic acid amide hydrazido betaine of the formula having a relative viscosity 1 of 1.93 was dissolved to a 27.5% by weight solution in dimethyl-formamide. The spinning procedure, the stretching and drying being carried out according to Example 1. Reversible longitudinal swelling: 6.6% (70 C.), 5.2% (130 C.). The same procedure was carried out with a 27% by weight solution of the copolymer and a 23% by weight solution of the acrylonitrile homopolymer. Reversibility of crimp: 46%.
• a bi-component fibre consisting of a homopolymer of acrylonitrile and a copolymer of acrylonitrile containing at least 70% by weight of acrylonitrile in combination with other polymerisable unsaturated compounds, using at most 20% by weight of a copolymerisable hydrazido betaine of the formula and A represents an aliphatic, aromatic or araliphatic radical having an unsaturated copolymerisable group, R is an alkylene radical and R and R" represent C to C -alky1 radicals which together with the nitrogen atom may form a heterocyclic ring system.
• a method for producing a bi-component fibre based on acrylonitrile polymers which comprises spinning in conjugated form a homopolymer of acrylonitrile with a copolymer of acrylonitrile, containing at least 70% by weight of acrylonitrile, and other copolymerisable compounds using at most 20% by weight of a copolymerisable hydrazidobetaine compound the formula:

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Artificial Filaments (AREA)
• Multicomponent Fibers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (8)

Cited By (3)

• 1967
  • 1967-01-10 CH CH33267A patent/CH491210A/de not_active IP Right Cessation
  • 1967-01-10 CH CH755770A patent/CH523991A/de not_active IP Right Cessation
  • 1967-01-10 CH CH755770D patent/CH755770A4/xx unknown
  • 1967-01-16 SE SE00624/67A patent/SE348505B/xx unknown
  • 1967-01-18 GB GB2670/67A patent/GB1148632A/en not_active Expired
  • 1967-01-26 US US611802A patent/US3470060A/en not_active Expired - Lifetime
  • 1967-01-27 NL NL6701367A patent/NL6701367A/xx unknown
  • 1967-01-31 ES ES0336290A patent/ES336290A1/es not_active Expired
  • 1967-02-02 FR FR93402A patent/FR1509844A/fr not_active Expired
  • 1967-02-02 BE BE693576D patent/BE693576A/xx unknown

Non-Patent Citations (1)

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