EP0953673B1 - Agents for and methods of processing synthetic fibers - Google Patents

Agents for and methods of processing synthetic fibers Download PDF

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Publication number
EP0953673B1
EP0953673B1 EP99303196A EP99303196A EP0953673B1 EP 0953673 B1 EP0953673 B1 EP 0953673B1 EP 99303196 A EP99303196 A EP 99303196A EP 99303196 A EP99303196 A EP 99303196A EP 0953673 B1 EP0953673 B1 EP 0953673B1
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Prior art keywords
carbon atoms
agent
group
weight
false twisting
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German (de)
French (fr)
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EP0953673A3 (en
EP0953673A2 (en
Inventor
Hisao Yamamoto
Fumihiko Kimura
Masahiro Nagaya
Yukiko Kitagawa
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Takemoto Oil and Fat Co Ltd
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Takemoto Oil and Fat Co Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • D02G1/026Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting in the presence of a crimp finish
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288Phosphonic or phosphonous acids or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/313Unsaturated compounds containing phosphorus atoms, e.g. vinylphosphonium compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating 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 nitrogen
    • D06M13/46Compounds containing quaternary nitrogen atoms
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53Polyethers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • This invention relates to agents for and methods of processing synthetic fibers.
  • an agent containing a lubricant and an antistatic agent is usually applied to them in order to provide them with lubricity and antistatic characteristic.
  • synthetic fibers are subjected to a heat treatment or, for example, to a false twisting process, however, it is important to prevent the contamination of heaters due to the thermal degradation of such agent during the heat treatment and to thereby prevent the generation of fuzz and occurrence of yarn breakage and to obtain false-twisted yarns of a high quality.
  • This invention relates to agents and methods with which such contamination of heaters can be effectively prevented.
  • polyorganosiloxane compound which may be mixed in such a prior art agent include (1) polydimethyl siloxane and fluoroalkyl modified polydimethyl polysiloxane with viscosity at 25°C greater than 30x10 -6 m 2 /s and surface tension at 25°C less than 28dyne/cm (See Japanese Patent Publication Tokkai 54-46923), (2) polydimethyl siloxane with viscosity at 30°C greater than 15x10 -6 m 2 /s (See Japanese Patent Publication Tokkai 48-53093), (3) phenyl polysiloxane with viscosity at 30°C in the range of 10x10 -6 -80x10 -6 m 2 /s (Japanese Patent Publication Tokko 47-50657)
  • This invention is based on the present inventors' discovery that the problem stated above can be obviated if use is made of an agent comprising a polyether compound, a straight-chain polyether modified polyorganosiloxane of a specified kind and an ionic surfactant, containing the straight-chain polyether modified polyorganosiloxane and the ionic surfactant at specified ratios and that such an agent should be applied at a specified ratio to synthetic fibers which are subjected to a heat treatment.
  • This invention relates to fiber processing agents comprising a polyether compound, a straight-chain polyether modified polyorganosiloxane shown by Formula (1) given below at a ratio of 0.1-12 weight % and an ionic surfactant at a ratio of 0.1-12 weight %:
  • R 1 and R 4 are each either a residual group obtained by removing active hydrogen from a monohydric compound containing active hydrogen and having 1-40 carbon atoms or hydroxyl group
  • R 2 and R 3 are each alkylene group with 3 or 4 carbon atoms
  • R 5 is alkyl group with 1-4 carbon atoms, fluoroalkyl group with 1-4 carbon atoms or phenyl group
  • a 1 and A 2 are each alkylene group with 2-4 carbon atoms
  • p and q are each an integer 2-200
  • m is an integer 3-200
  • n is an integer 1-30.
  • the invention also relates to a method of applying such an agent at a rate of 0.1-3 weight % of the synthetic fibers to be subjected to a heat treatment.
  • the end groups R 1 and R 4 of linear polyether units of Formula (1) may or may not be different from each other, each being either a residual group obtained by removing active hydrogen from a monohydric compound containing active hydrogen and having 1-40 carbon atoms or hydroxyl group.
  • Examples of such monohydric compound containing active hydrogen and having 1-40 carbon atoms include (1) aliphatic saturated alcohols with 1-40 carbon atoms such as methanol, octanol, stearyl alcohol, ceryl alcohol, isobutanol, 2-ethyl hexanol, isohexadecyl alcohol, isotetracosanyl alcohol, 2-propanol and 12-eicosanyl alcohol, (2) aliphatic unsaturated alcohols with 2-40 carbon atoms such as vinyl alcohol, propenyl alcohol, oleyl alcohol, eicosenyl alcohol, 2-methyl-2-propylene-1-ol and 15-hexadecene-2-ol, (3) phenol, (4) octyl phenols substituted by alkyl group with 1-34 carbon atoms such as propyl phenol, actyl phenol and tridecyl phenol, (5) aliphatic saturated thiols with 1-40 carbon atoms such
  • monohydric compounds containing active hydrogen and having alkoxy group with 1-10 carbon atoms formed from aliphatic saturated alcohol with 1-10 carbon atoms or alkenoxy group with 2-10 carbon atoms formed from aliphatic unsaturated alcohol with 2-10 carbon atoms are preferable.
  • a 1 and A 2 are alkylene groups with 2-4 carbon atoms.
  • alkylene group examples include ethylene group, propylene group, 1,2-butylene group and 1,4-butylene group. These alkylene groups may appear singly or in a mixed form but those with only ethylene groups and a mixture of ethylene and propylene groups are preferred. When ethylene and propylene groups are mixed, the manner of combination between oxyethylene units and oxypropylene units or combination between ethoxy units and propoxy units that are formed may be block combination or random combination.
  • the number p of the alkoxy units and the number q of the oxyalkylene units of Formula (1) are within the range of 2-200 but this range should preferably be 20-150 and more preferably 30-100.
  • R 5 inside the divalent siloxane unit is alkyl group with 1-4 carbon atoms, fluoroalkyl group with 1-4 carbon atoms or phenyl group.
  • alkyl group with 1-4 carbon atoms include methyl group, ethyl group, propyl group and butyl group.
  • fluoroalkyl group include not only partial fluorine substituted alkyl groups such as ⁇ -trifluoropropyl group and ⁇ , ⁇ -pentafluoropropyl group but also total fluorine substituted alkyl groups such as heptafluoropropyl group and pentafluoroethyl group, but methyl group is preferred.
  • the number m of the divalent siloxane units in Formula (1) is an integer between 3-200 but this range is preferably 5-20 and more preferably 6-14.
  • the connecting groups R 2 and R 3 between linear polyether units and linear polysiloxane units of Formula (1) are alkylene groups with 3 or 4 carbon atoms.
  • Such alkylene groups serving as a connecting group, having 3 or 4 carbons atoms contain a carbon atom directly connected to a silicon atom in a linear polysiloxane unit.
  • Examples of such alkylene group with 3 or 4 carbon atoms include trimethylene group, tetramethylene group, isopropylene group and isobutylene group, of which, however, trimethylene group, tetramethylene group and isobutylene group are preferred.
  • n of the units formed with linear polysiloxane units and linear polyether units is an integer between 1-30 but this range is preferably 1-9.
  • This invention is not limited by the method of synthesizing the straight chain polyether modified polyorganosiloxane to be used therein.
  • the method for the synthesis include (1) the method of reacting corresponding ⁇ , ⁇ -dihydrogen poly(partially substituted)dimethyl siloxane (1 mole) with one-end (meth)allyl polyalkoxylate (2 moles) with heating in the presence of chloroplatinic acid as catalyst, (2) the method of reacting corresponding ⁇ , ⁇ -dihydrogen poly(partially substituted)dimethyl siloxane (more than 2 moles) with both-end (meth)allyl polyalkoxylate (more than 2 moles) with heating in the presence of chloroplatinic acid as catalyst, and (3) the method of reacting corresponding ⁇ , ⁇ -dihydrogen poly(partially substituted)dimethyl siloxane (more than 2 moles) with both-end (meth)allyl polyalkoxylate (more than 2 moles) with heating in the
  • Quaternary onium salt shown by Formula (2) given below is an preferred example of the ionic surfactant: where X is N or P, R 6 , R 7 , R 8 and R 9 are each alkyl group with 1-25 carbon atoms, alkenyl group with 2-25 carbon atoms or hydroxyalkyl group with 1-6 carbon atoms, B y- is anion group of valence y obtained by removing hydrogen ion from a compound selected from acidic phosphoric acid esters with 1-30 carbon atoms, acidic sulfuric acid esters with 1-30 carbons atoms, acidic sulfonic acid esters with 1-30 carbon atoms and carboxylic acids with 1-30 carbon atoms, and y is an integer 1-3.
  • Examples of quaternary onium salt shown by Formula (2) include (1) those, for which X is N, comprising quaternary ammonium cation group and anion group obtained by removing hydrogen ions either partially or totally from the aforementioned compound with valence 1-3, and (2) those, for which X is P, comprising quaternary phosphonium cation group and anion group obtained by removing hydrogen ions either partially or totally from the aforementioned compound with valence 1-3.
  • quaternary ammonium salts examples include (1) those wherein R 6 -R 9 (hereinafter referred to as the organic groups of Formula (2)) are all alkyl group with 1-25 carbon atoms, (2) those wherein the organic groups of Formula (2) are all alkenyl group with 2-25 carbon atoms, (3) those wherein the organic groups of Formula (2) are all hydroxyalkyl group with 1-6 carbon atoms, (4) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms, (5) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, (6) those wherein some of the organic groups of Formula (2) are alkenyl group with 2-25 carbon atoms and the rest are hydroxyal
  • Examples of preferred quaternary ammonium cation group wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms include tetramethyl ammonium, triethylmethyl ammonium, tripropylethyl ammonium, tributylmethyl ammonium, tetrabutyl ammonium, triisooctylethyl ammonium, trimethyloctyl ammonium, dilauryl dimethyl ammonium and trimethylstearyl ammonium.
  • Examples of preferred quaternary ammonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms include dibutenyl diethyl ammonium, dimethyl dioleyl ammonium, trimethyloleyl ammonium and triethyl eicosenyl ammonium.
  • Examples of preferred quaternary ammonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms include tributylhydroxyethyl ammonium, di(hydroxyethyl) dipropyl ammonium, tri(hydroxyethyl) octyl ammonium and tri(hydroxypropyl) methyl ammonium.
  • organic groups of Formula (2) are all alkyl group with 1-12 carbon atoms
  • the anion groups forming the aforementioned quaternary ammonium salts are those obtained by partially or totally removing the hydrogen ions from the aforementioned compound with valence 1-3.
  • aliphatic phosphates with 1-26 carbon atoms aliphatic sulfonates with 1-26 carbon atoms and aliphatic carboxylic acids with 1-26 carbon atoms
  • aliphatic sulfonates with 8-24 carbon atoms and aliphatic carboxylic acids with 8-24 carbon atoms such as lauryl sulfonate, oleyl sulfonate, isostearic acid, oleic acid and pentadecenyl succinic acid.
  • This invention is not limited particularly by the method by which such quaternary ammonium salts to be used in this invention should be synthesized.
  • Examples of method for the synthesis include (1) method of reacting corresponding tertiary amine with trialkyl phosphate, (2) method of reacting corresponding tertiary amine with dialkyl sulfate, (3) method of reacting corresponding tertiary amine with ethylene oxide in the presence of water to obtain quaternary ammonium hydroxide and then reacting it with acidic sulfonic acid esters, and (4) method of reacting corresponding tertiary amine with alkyl halide to obtain quaternary ammonium halide and then reacting it with metallic salt of carboxylic acid.
  • quaternary phosphonium salts examples include, similarly to the description given above regarding quaternary ammonium cation groups, (1) those wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms, (2) those wherein the organic groups of Formula (2) are all alkenyl group with 2-25 carbon atoms, (3) those wherein the organic groups of Formula (2) are all hydroxyalkyl group with 1-6 carbon atoms, (4) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms, (5) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, (6) those wherein some of the organic groups of Formula (2) are alkenyl group with 2-25 carbon atoms and the
  • Examples of preferred quaternary phosphonium cation group wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms include tetramethyl phosphonium, tributylmethyl phosphonium, tetrabutyl phosphonium, methyl trioctyl phosphonium and lauryl trimethyl phosphonium.
  • Examples of preferred quaternary phosphonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms include trimethyloleyl phosphonium and oleyl tripropenyl phosphonium.
  • Examples of preferred quaternary phosphonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms include tributyl (2-hydroxyethyl) phosphonium and trioctyl (4-hydroxybutenyl) phosphonium. Particularly preferable are those wherein the organic groups of Formula (2) are all alkyl group with 1-4 carbon atoms, such as tributylmethyl phosphonium and tetrabutyl phosphonium.
  • This invention is not limited particularly by the method by which such quaternary phosphonium salts to be used in this invention should be synthesized.
  • Examples of method for the synthesis include (1) method of mixing metallic or ammonium salt of the corresponding organic acid with quaternary phosphonium salt inside a solvent and washing with water and separating the inorganic salt obtained as by-product, and (2) method of using an organic solvent such as methanol, isopropanol or acetone to carry out extraction.
  • Polyether compounds of known kinds such as disclosed in Japanese Patent Publication Tokkai 56-31077 and U.S. patent 4,561,987 may be used for the purpose of this invention.
  • Preferred examples of such polyether compound include polyether (poly)ols with oxyethylene units and oxypropylene units as principal constituent units such as polyether monool, polyether diol and polyether triol. Particularly preferable are those with average molecular weight of 700-20000.
  • Polyether compound within the context of this invention includes mixtures of polyether compounds with different molecular weights. When such a mixture is used, it is preferable to use a mixture with a polyether compound with average molecular weight of 1000-3000 and another with average molecular weight of 5000-15000.
  • the agents according to this invention are characterized as comprising a polyether compound, straight-chain polyether modified polyorganosiloxane and an ionic surfactant.
  • Straight-chain polyether modified polyorganosiloxane is to be contained at a ratio of 0.1-12 weight %, and the ionic surfactant is also to be contained at a ratio of 0.1-12 weight %, but it is preferred that straight-chain polyether modified polyorganosiloxane be contained at a ratio of 0.3-5 weight %, and quaternary onium salt of the kind described above as the ionic surfactant be contained at a ratio of 0.3-5 weight %.
  • an ester compound of a specified kind and/or an ether ester compound be further contained at a specified ratio.
  • the kind of ester compound is no particular limitation as long as the total number of carbon atoms is 10-50.
  • ester compound examples include (1) aliphatic monoesters of aliphatic alcohol and aliphatic carboxylic acid such as ethyl laurate, octyl laurate, isodecylstearate and oleyl docosenoate, and (2) aliphatic polyhydric esters of aliphatic alcohol and aliphatic carboxylic acid such as 1,4-butanediol dioctanate, dioleyl adipate, trimethylolethane diisostearate and glycerine trilaurate, but aliphatic monoesters with total number of carbon atoms 15-30 are preferable.
  • aliphatic monoesters of aliphatic alcohol and aliphatic carboxylic acid such as ethyl laurate, octyl laurate, isodecylstearate and oleyl docosenoate
  • ether ester compound there is no particular limitation as to the ether ester compound as long as the total number of carbon atoms is 10-50.
  • Many examples obtainable by reacting alkylene oxide with 2-4 carbon atoms with an ester compound as described above may be considered, but those with the total number of carbon atoms 20-40 obtainable by reacting monoester of aliphatic alcohol and aliphatic carboxylic acid with 1-10 moles of ethylene oxide are preferred.
  • the ratio is about 1-30 weight % of the agent.
  • Preferred ratios of mixing are 0.3-5 weight % for straight-chain polyether modified polyorganosiloxane, 0.3-5 weight % for quaternary onium salt as ionic surfactant, and 3-25 weight % for ester compound and/or ether ester compound, the remainder being polyether compound.
  • an agent as described above is applied to synthetic fibers to be subjected to a heat treatment at a ratio of 0.1-3 weight % and preferably 0.2-1 weight %.
  • the agent is applied to synthetic fiber filament yarns immediately after the spinning process, and these yarns are thereafter subjected to a heat treatment.
  • synthetic fibers acquire lubricity and hence the contamination of heaters used in the heat treatment can be effectively prevented.
  • heat treatment process include drawing process, twisting process, crimp-setting process and false twisting process, but the present invention is effective particularly when the synthetic fibers are subjected to a false twisting process.
  • Examples of false twisting apparatus include (1) apparatus of a contact heater type provided with a heater of temperature 150-230°C and length 150-250cm such that synthetic fiber filament yarns are passed in contact with and over a heater plate, and (2) apparatus of a short heater type provided with a heater with temperature 300-600°C and length 20-150cm such that synthetic fiber filament yarns travels over the heater plate without touching it.
  • the agents and methods of this invention are particularly effective, however, when used in a false twisting process by means of an apparatus provided with a short heater with temperature 350-550°C and length 20-140cm such that synthetic fiber filament yarns travel in contact with yarn path regulating device set inside the heater.
  • This invention imposes no particular limitation on the method of applying an agent of this invention on synthetic fibers.
  • Examples of method of application include conventional methods such as roller oiling method, guide oiling method by means of a measuring pump, lubrication by soaking and spray lubrication method, but roller oiling method and guide oiling method with a measuring pump are preferred.
  • an agent of this invention When an agent of this invention is applied to synthetic fibers, it may be done in the form of an aqueous emulsion, as a solution in an organic solvent or by itself, but it is preferred to use it as an aqueous emulsion. In such a situation, an emulsifier may be used appropriately, and it is preferable to prepare the aqueous emulsion so as to contain the agent at a ratio of 5-30 weight %.
  • other agents such as an antioxidant, an antiseptic and an anti-rusting agent may be applied at the same time, depending on the purpose, but the amount of their use should be as small as possible.
  • polyester fibers having ethylene terephthalate as its main structural unit examples include (1) polyester fibers having ethylene terephthalate as its main structural unit, (2) polyamide fibers such as nylon 6 and nylon 66, (3) polyacrylic fibers such as polyacrylonitrile and modacrylic fibers, and (4) polyolefins such as polyethylene and polypropylene.
  • This invention is particularly effective, however, when applied to partially drawn polyester yarns, partially drawn polyamide yarns or directly spun drawn polyester yarns.
  • Agent Test Example 1 was prepared by mixing 96 parts of polyether compound (P-1), 2 parts of straight-chain polyether modified polyorganosiloxane (MS-1) and 2 parts of ionic surfactant (QS-1). Other agents were similarly prepared. These are shown in Tables 1 and 2.
  • (MS-1)-(MS-4) and (PS-1)-(PS-7) are each straight-chain polyether modified polyorganosiloxane shown by Formula (1) and as explained in Table 3 wherein "B” indicates “block addition” and “R” indicates "random addition”.
  • (QS-1)-(QS-5) are each quaternary onium salt shown by Formula (2) and as explained in Table 4.
  • (FN-1) Sodium isostearate.
  • ES-1) Octyl laurate
  • EE-2 Ester of octyloxypolyalkoxylate (polyalkoxylate being random connection of 5 ethoxy units and 3 propoxy units) and lauric acid.
  • cr-1) Linear polydimethylsiloxane with average molecular weight 3000.
  • (cr-2) Linear polyorganosiloxane with 2 methyl-phenyl siloxane units and 20 dimethylsiloxane units connected linearly.
  • (cr-3) Pendant-type polyether modified polyorganosiloxane with 140 dimethyl siloxane units and 8 siloxane units having polyether groups randomly connected linearly by siloxane-bonding, the polyether groups each consisting of random connection of 80 oxyethylene units and 20 oxypropylene units.
  • (cr-4) Pendant-type polyether modified polyorganosiloxane with average molecular weight 8600, having dimethylsiloxane units and siloxane units with polyether groups randomly connected linearly by siloxane-bonding, polyether groups contained by 92 weight %, the polyether groups each consisting of random connection of 15 oxyethylene units and 15 oxypropylene units.
  • Part 2 Application to partially drawn polyester filament yarns
  • aqueous emulsions with concentration of agent 15%.
  • polyethylene terephthalate chips with intrinsic viscosity 0.64 and containing titanium oxide by 0.2% were dried by a usual method, an extruder was used for spinning at 295°C.
  • the aqueous emulsions were applied by a roller oiling method to the traveling yarns after they were extruded from the spinneret and cooled to be hardened. They were wound up at the speed of 3300m/minute without mechanical drawing to obtain wound 10kg cakes of partially drawn 150-denier, 72-filament yarns with agents adhered at ratios shown in Tables 5 and 6.
  • Twisting system Three-axis disk friction method (with one guide disk on entrance side, one guide disk on exit side and seven hard polyurethane disks)
  • the heater tar on the yarn path on the surface of the heater on the twist side was removed by a brush, collected and weighed. The weights were measured for ten spindles, and the results are shown as the average weight (mg) per spindle.
  • Part 3 Application to partially drawn nylon filament yarns
  • aqueous emulsions with concentration of agent 10%.
  • nylon-6,6 chips with sulfuric acid relative viscosity 2.4 containing titanium oxide by 0.1% were dried by a usual method, an extruder was used for spinning at 290°C.
  • the aqueous emulsions were applied by a guide oiling method to the traveling yarns after they were extruded from the spinneret and cooled to be hardened. They were wound up at the speed of 4000m/minute without mechanical drawing to obtain wound 8kg cakes of partially drawn 70-denier, 24-filament yarns with agents adhered at ratios shown in Table 7.
  • Part 4 Application to directly spun drawn polyester filament yarns
  • aqueous emulsions with concentration of agent 10%.
  • the emulsions were applied to the running yarns of polyester filaments by the guide oiling method and the yarns were wound up by means of a first godet roller rotating at the rate of 3000m/minute, drawn mechanically between the second godet roller and wound up at the rate of 5000m/minute to obtain wound 5kg cakes of 75-denier, 36-filament directly spun drawn yarns with agents adhered at ratio of 0.35% with respect to the yarns.
  • agents and methods according to the present invention are capable of sufficiently prevent the contamination of heaters for processing synthetic fibers even if the process is for false twisting including a severe heat treatment.

Description

    Background of the Invention
  • This invention relates to agents for and methods of processing synthetic fibers.
  • During the course of production and processing of synthetic fibers, an agent containing a lubricant and an antistatic agent is usually applied to them in order to provide them with lubricity and antistatic characteristic. When the synthetic fibers are subjected to a heat treatment or, for example, to a false twisting process, however, it is important to prevent the contamination of heaters due to the thermal degradation of such agent during the heat treatment and to thereby prevent the generation of fuzz and occurrence of yarn breakage and to obtain false-twisted yarns of a high quality. This invention relates to agents and methods with which such contamination of heaters can be effectively prevented.
  • As an agent for preventing such contamination of heaters, it has been known to use a mixture of a polyether compound, a polyorganosiloxane compound and an ionic surfactant. Examples of polyorganosiloxane compound which may be mixed in such a prior art agent include (1) polydimethyl siloxane and fluoroalkyl modified polydimethyl polysiloxane with viscosity at 25°C greater than 30x10-6m2/s and surface tension at 25°C less than 28dyne/cm (See Japanese Patent Publication Tokkai 54-46923), (2) polydimethyl siloxane with viscosity at 30°C greater than 15x10-6m2/s (See Japanese Patent Publication Tokkai 48-53093), (3) phenyl polysiloxane with viscosity at 30°C in the range of 10x10-6-80x10-6m2/s (Japanese Patent Publication Tokko 47-50657), (4) polyether modified polyorganosiloxane (U.S. patents 4,561,987 and 5,061,384), (5) linear polyorganosiloxane with 4-12 siloxane units (U.S. patent 5,772,910), and (6) ring-like polyorganosiloxane with 4-14 siloxane units (U.S. patent 5,755,984). With these prior art agents, however, contamination of heaters during a heat treatment cannot be prevented sufficiently. In the case of a false twisting process using short heaters of a recently developed kind for heat treatments at temperatures over 300°C, in particular, the contamination of heaters could not be prevented satisfactorily. As explained above, if the contamination of heaters cannot be prevented to a satisfactory degree in the heat treatment process, fuzz and yarn breakage will take place and it is not possible to produce yarns with a high quality.
  • Summary of the Invention
  • The problem to be solved by this invention is that prior art agents could not satisfactorily prevent the contamination of heaters for heat treatment and in particular for an false twisting process using short heaters operating at temperatures above 300°C.
  • This invention is based on the present inventors' discovery that the problem stated above can be obviated if use is made of an agent comprising a polyether compound, a straight-chain polyether modified polyorganosiloxane of a specified kind and an ionic surfactant, containing the straight-chain polyether modified polyorganosiloxane and the ionic surfactant at specified ratios and that such an agent should be applied at a specified ratio to synthetic fibers which are subjected to a heat treatment.
  • Detailed Description of the Invention
  • This invention relates to fiber processing agents comprising a polyether compound, a straight-chain polyether modified polyorganosiloxane shown by Formula (1) given below at a ratio of 0.1-12 weight % and an ionic surfactant at a ratio of 0.1-12 weight %:
    Figure 00020001
    where R1 and R4 are each either a residual group obtained by removing active hydrogen from a monohydric compound containing active hydrogen and having 1-40 carbon atoms or hydroxyl group; R2 and R3 are each alkylene group with 3 or 4 carbon atoms, R5 is alkyl group with 1-4 carbon atoms, fluoroalkyl group with 1-4 carbon atoms or phenyl group, A1 and A2 are each alkylene group with 2-4 carbon atoms, p and q are each an integer 2-200, m is an integer 3-200 and n is an integer 1-30.
  • The invention also relates to a method of applying such an agent at a rate of 0.1-3 weight % of the synthetic fibers to be subjected to a heat treatment.
  • Examples of straight-chain polyether modified polyorganosiloxane shown by Formula (1) include (1) those, for which n = 1, of a structure having one linear polyether unit connected as a straight chain at each end of one linear polysiloxane unit through a connecting group such that both ends are a linear polyether unit, and (2) those, for which n = 2-30, of a structure having two or more linear polysiloxane units and two or more linear polyether units connected as a straight chain through a connecting group such that both ends are a linear polyether unit.
  • The end groups R1 and R4 of linear polyether units of Formula (1) may or may not be different from each other, each being either a residual group obtained by removing active hydrogen from a monohydric compound containing active hydrogen and having 1-40 carbon atoms or hydroxyl group. Examples of such monohydric compound containing active hydrogen and having 1-40 carbon atoms include (1) aliphatic saturated alcohols with 1-40 carbon atoms such as methanol, octanol, stearyl alcohol, ceryl alcohol, isobutanol, 2-ethyl hexanol, isohexadecyl alcohol, isotetracosanyl alcohol, 2-propanol and 12-eicosanyl alcohol, (2) aliphatic unsaturated alcohols with 2-40 carbon atoms such as vinyl alcohol, propenyl alcohol, oleyl alcohol, eicosenyl alcohol, 2-methyl-2-propylene-1-ol and 15-hexadecene-2-ol, (3) phenol, (4) octyl phenols substituted by alkyl group with 1-34 carbon atoms such as propyl phenol, actyl phenol and tridecyl phenol, (5) aliphatic saturated thiols with 1-40 carbon atoms such as octane thiol, octadecan thiol, 2-ethylhexane thiol and isododecan thiol, (6) aliphatic saturated carboxylic acids with 1-40 carbon atoms such as acetic acid, lauric acid and behenic acid, (7) aliphatic unsaturated carboxylic acids with 2-40 carbon atoms such as oleic acid, erucic acid and linoleic acid, (8) aliphatic alkylamines with 2-40 carbon atoms such as butylamine and dioleylamine, and (9) aliphatic alkanolamines with 4-40 carbon atoms such as dibutyl ethanolamine and diisostearyl propylamine. Of these, monohydric compounds containing active hydrogen and having alkoxy group with 1-10 carbon atoms formed from aliphatic saturated alcohol with 1-10 carbon atoms or alkenoxy group with 2-10 carbon atoms formed from aliphatic unsaturated alcohol with 2-10 carbon atoms are preferable.
  • In Formula (1), A1 and A2 are alkylene groups with 2-4 carbon atoms. Examples of such alkylene group include ethylene group, propylene group, 1,2-butylene group and 1,4-butylene group. These alkylene groups may appear singly or in a mixed form but those with only ethylene groups and a mixture of ethylene and propylene groups are preferred. When ethylene and propylene groups are mixed, the manner of combination between oxyethylene units and oxypropylene units or combination between ethoxy units and propoxy units that are formed may be block combination or random combination.
  • The number p of the alkoxy units and the number q of the oxyalkylene units of Formula (1) are within the range of 2-200 but this range should preferably be 20-150 and more preferably 30-100.
  • In Formula (1), R5 inside the divalent siloxane unit is alkyl group with 1-4 carbon atoms, fluoroalkyl group with 1-4 carbon atoms or phenyl group. Examples of such alkyl group with 1-4 carbon atoms include methyl group, ethyl group, propyl group and butyl group. Examples of fluoroalkyl group include not only partial fluorine substituted alkyl groups such as γ-trifluoropropyl group and β,γ-pentafluoropropyl group but also total fluorine substituted alkyl groups such as heptafluoropropyl group and pentafluoroethyl group, but methyl group is preferred.
  • The number m of the divalent siloxane units in Formula (1) is an integer between 3-200 but this range is preferably 5-20 and more preferably 6-14.
  • The connecting groups R2 and R3 between linear polyether units and linear polysiloxane units of Formula (1) are alkylene groups with 3 or 4 carbon atoms. Such alkylene groups serving as a connecting group, having 3 or 4 carbons atoms, contain a carbon atom directly connected to a silicon atom in a linear polysiloxane unit. Examples of such alkylene group with 3 or 4 carbon atoms include trimethylene group, tetramethylene group, isopropylene group and isobutylene group, of which, however, trimethylene group, tetramethylene group and isobutylene group are preferred.
  • The number n of the units formed with linear polysiloxane units and linear polyether units is an integer between 1-30 but this range is preferably 1-9.
  • This invention is not limited by the method of synthesizing the straight chain polyether modified polyorganosiloxane to be used therein. Examples of the method for the synthesis include (1) the method of reacting corresponding α,ω-dihydrogen poly(partially substituted)dimethyl siloxane (1 mole) with one-end (meth)allyl polyalkoxylate (2 moles) with heating in the presence of chloroplatinic acid as catalyst, (2) the method of reacting corresponding α,ω-dihydrogen poly(partially substituted)dimethyl siloxane (more than 2 moles) with both-end (meth)allyl polyalkoxylate (more than 2 moles) with heating in the presence of chloroplatinic acid as catalyst, and (3) the method of reacting corresponding α,ω-dihydrogen poly(partially substituted)dimethyl siloxane (more than 2 moles) with both-end (meth)allyl polyalkoxylate (more than 2 moles) with heating in the presence of chloroplatinic acid as catalyst and causing the dimethylsilyl group of the compound thus obtained, having linear polysiloxane units at the ends, to react with one-end (meth)allyl polyalkoxylate.
  • Examples of the ionic surfactant which may be used according to this invention include known kinds of anionic surfactants, cationic surfactants and ampholitic surfactants. Quaternary onium salt shown by Formula (2) given below is an preferred example of the ionic surfactant:
    Figure 00050001
    where X is N or P, R6, R7, R8 and R9 are each alkyl group with 1-25 carbon atoms, alkenyl group with 2-25 carbon atoms or hydroxyalkyl group with 1-6 carbon atoms, By- is anion group of valence y obtained by removing hydrogen ion from a compound selected from acidic phosphoric acid esters with 1-30 carbon atoms, acidic sulfuric acid esters with 1-30 carbons atoms, acidic sulfonic acid esters with 1-30 carbon atoms and carboxylic acids with 1-30 carbon atoms, and y is an integer 1-3.
  • Examples of quaternary onium salt shown by Formula (2) include (1) those, for which X is N, comprising quaternary ammonium cation group and anion group obtained by removing hydrogen ions either partially or totally from the aforementioned compound with valence 1-3, and (2) those, for which X is P, comprising quaternary phosphonium cation group and anion group obtained by removing hydrogen ions either partially or totally from the aforementioned compound with valence 1-3.
  • First, quaternary ammonium salts according to this invention will be explained more in detail. Examples of quaternary ammonium cation group forming quaternary ammonium salts include (1) those wherein R6-R9 (hereinafter referred to as the organic groups of Formula (2)) are all alkyl group with 1-25 carbon atoms, (2) those wherein the organic groups of Formula (2) are all alkenyl group with 2-25 carbon atoms, (3) those wherein the organic groups of Formula (2) are all hydroxyalkyl group with 1-6 carbon atoms, (4) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms, (5) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, (6) those wherein some of the organic groups of Formula (2) are alkenyl group with 2-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, and (7) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms, some of the others are alkenyl group with 2-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms.
  • Examples of preferred quaternary ammonium cation group wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms include tetramethyl ammonium, triethylmethyl ammonium, tripropylethyl ammonium, tributylmethyl ammonium, tetrabutyl ammonium, triisooctylethyl ammonium, trimethyloctyl ammonium, dilauryl dimethyl ammonium and trimethylstearyl ammonium. Examples of preferred quaternary ammonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms include dibutenyl diethyl ammonium, dimethyl dioleyl ammonium, trimethyloleyl ammonium and triethyl eicosenyl ammonium. Examples of preferred quaternary ammonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms include tributylhydroxyethyl ammonium, di(hydroxyethyl) dipropyl ammonium, tri(hydroxyethyl) octyl ammonium and tri(hydroxypropyl) methyl ammonium. Particularly preferable are those wherein the organic groups of Formula (2) are all alkyl group with 1-12 carbon atoms, those wherein some of the organic groups of Formula (2) are alkenyl group with 16-22 carbon atoms and the rest are alkyl group with 1-12 carbon atoms, and those wherein some of the organic groups of Formula (2) are hydroxyalkyl group with 2-4 carbon atoms and the rest are alkyl group with 1-12 carbon atoms, such as tributylmethyl ammonium, tetrabutyl ammonium, trimethyloleyl ammonium and di(hydroxyethyl) methyloctyl ammonium.
  • The anion groups forming the aforementioned quaternary ammonium salts are those obtained by partially or totally removing the hydrogen ions from the aforementioned compound with valence 1-3. Examples of such compound with valence 1-3 include (1) acidic phosphoric acid esters with 1-30 carbon atoms such as methyl phosphate, diethyl phosphate, dioctyl phosphate, methyloleyl phosphate and nonylphenyl oxyethoxyethyl·methyl phosphate, (2) acidic sulfuric acid esters with 1-30 carbon atoms such as methyl sulfate, ethyl sulfate, lauryl sulfate and octylphenyloxypolyethoxy (the repetition number of ethoxy units being 3, or n=3) ethyl sulfate, (3) acidic sulfonic acid esters with 1-30 carbon atoms such as butyl sulfonate, lauryl sulfonate, stearyl sulfonate, dodecylphenyl sulfonate, oleylphenyl sulfonate, naphthyl sulfonate and diisopropylnaphthyl sulfonate, and (4) carboxylic acids with 1-30 carbons atoms including aliphatic monocarboxylic acids such as acetic acid, caproic acid, lauric acid, 2-ethylhexanoic acid, isostearic acid, oleic acid and erucic acid, aliphatic dicarboxylic acids such as malonic acid, adipic acid, sebacic acid and pentadecenyl succinic acid, aromatic carboxylic acids with 1-30 carbon atoms such as benzoic acid, phthalic acid and trimellitic acid, aliphatic hydroxy carboxylic acids such as lactic acid, ricinoleic acid and 12-hydroxystearic acid, and sulphur-containing aliphatic carboxylic acids with 1-30 carbon atoms such as thio-dipropionic acid. Preferable among these are aliphatic phosphates with 1-26 carbon atoms, aliphatic sulfonates with 1-26 carbon atoms and aliphatic carboxylic acids with 1-26 carbon atoms, and still more preferable among these are aliphatic sulfonates with 8-24 carbon atoms and aliphatic carboxylic acids with 8-24 carbon atoms such as lauryl sulfonate, oleyl sulfonate, isostearic acid, oleic acid and pentadecenyl succinic acid.
  • This invention is not limited particularly by the method by which such quaternary ammonium salts to be used in this invention should be synthesized. Examples of method for the synthesis include (1) method of reacting corresponding tertiary amine with trialkyl phosphate, (2) method of reacting corresponding tertiary amine with dialkyl sulfate, (3) method of reacting corresponding tertiary amine with ethylene oxide in the presence of water to obtain quaternary ammonium hydroxide and then reacting it with acidic sulfonic acid esters, and (4) method of reacting corresponding tertiary amine with alkyl halide to obtain quaternary ammonium halide and then reacting it with metallic salt of carboxylic acid.
  • Next, quaternary phosphonium salts according to this invention will be explained. Examples of quaternary phosphonium cation group forming quaternary phosphonium salts include, similarly to the description given above regarding quaternary ammonium cation groups, (1) those wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms, (2) those wherein the organic groups of Formula (2) are all alkenyl group with 2-25 carbon atoms, (3) those wherein the organic groups of Formula (2) are all hydroxyalkyl group with 1-6 carbon atoms, (4) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms, (5) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, (6) those wherein some of the organic groups of Formula (2) are alkenyl group with 2-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms, and (7) those wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms, some of the others are alkenyl group with 2-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms.
  • Examples of preferred quaternary phosphonium cation group wherein the organic groups of Formula (2) are all alkyl group with 1-25 carbon atoms include tetramethyl phosphonium, tributylmethyl phosphonium, tetrabutyl phosphonium, methyl trioctyl phosphonium and lauryl trimethyl phosphonium. Examples of preferred quaternary phosphonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are alkenyl group with 2-25 carbon atoms include trimethyloleyl phosphonium and oleyl tripropenyl phosphonium. Examples of preferred quaternary phosphonium cation group wherein some of the organic groups of Formula (2) are alkyl group with 1-25 carbon atoms and the rest are hydroxyalkyl group with 1-6 carbon atoms include tributyl (2-hydroxyethyl) phosphonium and trioctyl (4-hydroxybutenyl) phosphonium. Particularly preferable are those wherein the organic groups of Formula (2) are all alkyl group with 1-4 carbon atoms, such as tributylmethyl phosphonium and tetrabutyl phosphonium.
  • The anion groups forming these quaternary phosphonium salts are the same as those described above for forming quaternary ammonium salts.
  • This invention is not limited particularly by the method by which such quaternary phosphonium salts to be used in this invention should be synthesized. Examples of method for the synthesis include (1) method of mixing metallic or ammonium salt of the corresponding organic acid with quaternary phosphonium salt inside a solvent and washing with water and separating the inorganic salt obtained as by-product, and (2) method of using an organic solvent such as methanol, isopropanol or acetone to carry out extraction.
  • Polyether compounds of known kinds such as disclosed in Japanese Patent Publication Tokkai 56-31077 and U.S. patent 4,561,987 may be used for the purpose of this invention. Preferred examples of such polyether compound include polyether (poly)ols with oxyethylene units and oxypropylene units as principal constituent units such as polyether monool, polyether diol and polyether triol. Particularly preferable are those with average molecular weight of 700-20000. "Polyether compound" within the context of this invention includes mixtures of polyether compounds with different molecular weights. When such a mixture is used, it is preferable to use a mixture with a polyether compound with average molecular weight of 1000-3000 and another with average molecular weight of 5000-15000.
  • As described above, the agents according to this invention are characterized as comprising a polyether compound, straight-chain polyether modified polyorganosiloxane and an ionic surfactant. Straight-chain polyether modified polyorganosiloxane is to be contained at a ratio of 0.1-12 weight %, and the ionic surfactant is also to be contained at a ratio of 0.1-12 weight %, but it is preferred that straight-chain polyether modified polyorganosiloxane be contained at a ratio of 0.3-5 weight %, and quaternary onium salt of the kind described above as the ionic surfactant be contained at a ratio of 0.3-5 weight %.
  • In addition to a polyether compound, straight-chain polyether modified polyorganosiloxane and an ionic surfactant, it is preferred that an ester compound of a specified kind and/or an ether ester compound be further contained at a specified ratio. There is no particular limitation as to the kind of ester compound as long as the total number of carbon atoms is 10-50. Examples of such ester compound include (1) aliphatic monoesters of aliphatic alcohol and aliphatic carboxylic acid such as ethyl laurate, octyl laurate, isodecylstearate and oleyl docosenoate, and (2) aliphatic polyhydric esters of aliphatic alcohol and aliphatic carboxylic acid such as 1,4-butanediol dioctanate, dioleyl adipate, trimethylolethane diisostearate and glycerine trilaurate, but aliphatic monoesters with total number of carbon atoms 15-30 are preferable.
  • There is no particular limitation as to the ether ester compound as long as the total number of carbon atoms is 10-50. Many examples obtainable by reacting alkylene oxide with 2-4 carbon atoms with an ester compound as described above may be considered, but those with the total number of carbon atoms 20-40 obtainable by reacting monoester of aliphatic alcohol and aliphatic carboxylic acid with 1-10 moles of ethylene oxide are preferred.
  • When such ester compound and/or ether ester compound is added, the ratio is about 1-30 weight % of the agent. Preferred ratios of mixing are 0.3-5 weight % for straight-chain polyether modified polyorganosiloxane, 0.3-5 weight % for quaternary onium salt as ionic surfactant, and 3-25 weight % for ester compound and/or ether ester compound, the remainder being polyether compound.
  • According to the method of this invention, an agent as described above is applied to synthetic fibers to be subjected to a heat treatment at a ratio of 0.1-3 weight % and preferably 0.2-1 weight %. Normally, the agent is applied to synthetic fiber filament yarns immediately after the spinning process, and these yarns are thereafter subjected to a heat treatment. With an agent of this invention thus applied, synthetic fibers acquire lubricity and hence the contamination of heaters used in the heat treatment can be effectively prevented. Examples of heat treatment process include drawing process, twisting process, crimp-setting process and false twisting process, but the present invention is effective particularly when the synthetic fibers are subjected to a false twisting process. Examples of false twisting apparatus include (1) apparatus of a contact heater type provided with a heater of temperature 150-230°C and length 150-250cm such that synthetic fiber filament yarns are passed in contact with and over a heater plate, and (2) apparatus of a short heater type provided with a heater with temperature 300-600°C and length 20-150cm such that synthetic fiber filament yarns travels over the heater plate without touching it. The agents and methods of this invention are particularly effective, however, when used in a false twisting process by means of an apparatus provided with a short heater with temperature 350-550°C and length 20-140cm such that synthetic fiber filament yarns travel in contact with yarn path regulating device set inside the heater.
  • This invention imposes no particular limitation on the method of applying an agent of this invention on synthetic fibers. Examples of method of application include conventional methods such as roller oiling method, guide oiling method by means of a measuring pump, lubrication by soaking and spray lubrication method, but roller oiling method and guide oiling method with a measuring pump are preferred.
  • When an agent of this invention is applied to synthetic fibers, it may be done in the form of an aqueous emulsion, as a solution in an organic solvent or by itself, but it is preferred to use it as an aqueous emulsion. In such a situation, an emulsifier may be used appropriately, and it is preferable to prepare the aqueous emulsion so as to contain the agent at a ratio of 5-30 weight %. When the agent is applied to synthetic fibers, other agents such as an antioxidant, an antiseptic and an anti-rusting agent may be applied at the same time, depending on the purpose, but the amount of their use should be as small as possible.
  • Examples of synthetic fibers to which the agents and methods of this invention can be applied include (1) polyester fibers having ethylene terephthalate as its main structural unit, (2) polyamide fibers such as nylon 6 and nylon 66, (3) polyacrylic fibers such as polyacrylonitrile and modacrylic fibers, and (4) polyolefins such as polyethylene and polypropylene. This invention is particularly effective, however, when applied to partially drawn polyester yarns, partially drawn polyamide yarns or directly spun drawn polyester yarns.
  • The invention is described next by way of the following 52 embodiments. Details of the polyether compound, straight-chain polyether modified polyorganosiloxane, ionic surfactant, ester compound and ether ester compound which are used in these embodiments will be described further below.
  • (1) The agent contains polyether compound (P-1) by 96 weight %, straight-chain polyether modified polyorganosiloxane (MS-1) by 2 weight % and ionic surfactant (QS-1) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (2) The agent in Embodiment (1) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (3) The agent contains polyether compound (P-1) by 94 weight %, straight-chain polyether modified polyorganosiloxane (MS-1) by 2 weight % and ionic surfactant (QS-1) by 4 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (4) The agent in Embodiment (3) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (5) The agent contains polyether compound (P-2) by 82 weight %, straight-chain polyether modified polyorganosiloxane (MS-2) by 3 weight %, ionic surfactant (QS-2) by 1 weight %, ester compound (ES-1) by 4 weight % and ether ester compound (EE-1) by 10 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (6) The agent in Embodiment (5) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (7) The agent contains polyether compound (P-1) by 95 weight %, straight-chain polyether modified polyorganosiloxane (PS-1) by 3 weight % and ionic surfactant (QS-3) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (8) The agent in Embodiment (7) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (9) The agent contains polyether compound (P-1) by 90 weight %, straight-chain polyether modified polyorganosiloxane (PS-2) by 4 weight %, ionic surfactant (QS-4) by 1 weight %, and ether ester compound (EE-2) by 5 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (10) The agent in Embodiment (9) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (11) The agent contains polyether compound (P-1) by 93 weight %, straight-chain polyether modified polyorganosiloxane (PS-2) by 4 weight %, and ionic surfactant (QS-4) by 3 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (12) The agent in Embodiment (11) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (13) The agent contains polyether compound (P-1) by 96 weight %, straight-chain polyether modified polyorganosiloxane (PS-3) by 2 weight %, and ionic surfactant (QS-5) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (14) The agent in Embodiment (13) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (15) The agent contains polyether compound (P-1) by 93 weight %, straight-chain polyether modified polyorganosiloxane (PS-4) by 5 weight %, and ionic surfactant (FN-1) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (16) The agent in Embodiment (15) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (17) The agent contains polyether compound (P-1) by 93 weight %, straight-chain polyether modified polyorganosiloxane (PS-5) by 5 weight %, and ionic surfactant (PA-1) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (18) The agent in Embodiment (17) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (19) The agent contains polyether compound (P-2) by 98.5 weight %, straight-chain polyether modified polyorganosiloxane (PS-2) by 0.5 weight %, and ionic surfactant (QS-4) by 1 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.8 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (20) The agent in Embodiment (19) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.8 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (21) The agent contains polyether compound (P-1) by 93 weight %, straight-chain polyether modified polyorganosiloxane (TS-1) by 5 weight %, and ionic surfactant (QS-1) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (22) The agent in Embodiment (21) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (23) The agent contains polyether compound (P-2) by 93 weight %, straight-chain polyether modified polyorganosiloxane (TS-2) by 2 weight %, and ionic surfactant (QS-2) by 5 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (24) The agent in Embodiment (23) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a falsi twisting apparatus with a short heater at temperature 510°C.
  • (25) The agent contains polyether compound (P-2) by 96 weight %, straight-chain polyether modified polyorganosiloxane (TS-3) by 2 weight %, and ionic surfactant (QS-3) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (26) The agent in Embodiment (25) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.4 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (27) The agent contains polyether compound (P-1) by 90 weight %, straight-chain polyether modified polyorganosiloxane (MS-3) by 1 weight %, ionic surfactant (QS-4) by 7 weight % and ester compound (ES-1) by 2 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (28) The agent in Embodiment (27) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (29) The agent contains polyether compound (P-1) by 89 weight %, straight-chain polyether modified polyorganosiloxane (MS-4) by 1 weight %, and ionic surfactant (QS-5) by 10 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (30) The agent in Embodiment (29) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (31) The agent contains polyether compound (P-1) by 91 weight %, straight-chain polyether modified polyorganosiloxane (PS-6) by 6 weight %, and ionic surfactant (QS-1) by 3 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (32) The agent in Embodiment (31) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (33) The agent contains polyether compound (P-1) by 88 weight %, straight-chain polyether modified polyorganosiloxane (PS-7) by 9 weight %, and ionic surfactant (FN-1) by 3 weight %. An aqueous emulsion is obtained with this agent and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (34) The agent in Embodiment (33) is made into an aqueous emulsion and after it is applied to partially drawn polyester yarns at a ratio of 0.3 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (35) The agent in Embodiment (5) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.50 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C. (36) The agent in Embodiment (5) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.50 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 460°C.
  • (37) The agent in Embodiment (7) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.55 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (38) The agent in Embodiment (7) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.55 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 460°C.
  • (39) The agent in Embodiment (9) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.45 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (40) The agent in Embodiment (9) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.45 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 460°C.
  • (41) The agent in Embodiment (19) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.65 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (42) The agent in Embodiment (19) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.65 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 460°C.
  • (43) The agent in Embodiment (21) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.55 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (44) The agent in Embodiment (21) is made into an aqueous emulsion and after it is applied to partially drawn nylon filament yarns at a ratio of 0.55 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 460°C.
  • (45) The agent in Embodiment (5) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (46) The agent in Embodiment (5) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (47) The agent in Embodiment (9) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (48) The agent in Embodiment (9) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (49) The agent in Embodiment (15) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (50) The agent in Embodiment (15) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • (51) The agent in Embodiment (23) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus of a contact heater type with heater temperature 210°C.
  • (52) The agent in Embodiment (23) is made into an aqueous emulsion and after it is applied to directly spun polyester drawn yarns at a ratio of 0.35 weight % as the agent, the yarns are subjected to a false twisting process by means of a false twisting apparatus with a short heater at temperature 510°C.
  • In what follows, the invention and its effects will be described with reference to test examples and comparison examples, but these test examples are not intended to limit the scope of this invention. In the following, "parts" shall mean "weight parts" and "%" shall mean "weight %".
  • Examples Part 1 (Preparation of agents)
  • Agent Test Example 1 was prepared by mixing 96 parts of polyether compound (P-1), 2 parts of straight-chain polyether modified polyorganosiloxane (MS-1) and 2 parts of ionic surfactant (QS-1). Other agents were similarly prepared. These are shown in Tables 1 and 2.
    Polyether Compound Straight-chain Polyether Modified Polyorganosiloxane Ionic Surfactant Others
    Kind Amount Kind Amount Kind Amount Kind Amount
    Test Examples
    1 P-1 96 MS-1 2 QS-1 2
    2 P-1 94 MS-2 2 QS-1 4
    3 P-1 82 MS-2 3 QS-2 1 ES-1 4
    EE-1 10
    4 P-1 95 PS-1 3 QS-3 2
    5 P-1 90 PS-2 4 QS-4 1 EE-2 5
    6 P-1 93 PS-2 4 QS-4 3
    7 P-1 96 PS-3 2 QS-5 2
    8 P-1 93 PS-4 5 FN-1 2
    9 P-1 93 PS-5 5 PA-1 2
    10 P-2 98.5 PS-2 0.5 QS-4 1
    11 P-1 93 TS-1 5 QS-1 2
    12 P-2 93 TS-2 2 QS-2 5
    13 P-2 96 TS-3 2 QS-3 2
    14 P-1 90 MS-3 1 QS-4 7 ES-1 2
    15 P-1 89 MS-4 1 QS-5 10
    16 P-1 91 PS-6 6 QS-1 3
    17 P-1 88 PS-7 9 FN-1 3
    18 P-3 96 MS-1 3 QS-1 1
    19 P-4 86 PS-1 2 QS-6 2 EE-1 10
    Polyether Compound Straight-chain Polyether Modified Polyorganosiloxane Ionic Surfactant Others
    Kind Amount Kind Amount Kind Amount Kind Amount
    Comparison Examples
    1 P-1 95.95 MS-2 0.05 QS-1 4
    2 P-1 95.95 PS-2 4 QS-1 0.05
    3 P-1 81 MS-2 15 QS-1 4
    4 P-1 81 PS-2 4 QS-1 15
    5 P-1 93 QS-1 2 cr-1 5
    6 P-1 93 QS-2 2 cr-2 5
    7 P-1 90 QS-3 5 cr-3 5
    8 P-1 95 QS-4 2 cr-3 3
    9 P-1 92 QS-5 3 cr-4 5
    10 P-1 98 QS-5 2
    11 P-2 94 QS-1 2 cr-1 4
    12 P-2 93 QS-2 3 cr-2 4
    13 P-2 92 FN-1 5 cr-3 3
    14 P-2 94 PA-1 2 cr-4 4
    15 PS-2 50 QS-4 50
    16 P-3 95.95 MS-3 0.05 QS-1 4
    In Tables 1 and 2:
       Amount: Used amount in weight %
       (P-1): Mixture of 70 parts of methoxy polyalkylene glycol ether with average molecular weight 2000 with block addition of oxyethylene units and oxypropylene units at molar ratio of 80/20 and 30 parts of polyalkylene glycol ether with average molecular weight 8000 with random addition of oxyethylene units and oxypropylene units at molar ratio of 20/80.
       (P-2): Mixture of 50 parts of dodecyloxy polyalkylene glycol ether with average molecular weight 2000 with block addition of oxyethylene units and oxypropylene units at molar ratio of 80/20, 40 parts of butoxy polyalkylene glycol ether with average molecular weight 2500 with random addition of oxyethylene units and oxypropylene units at molar ratio of 40/60, and 10 parts of polyalkylene glycol ether with average molecular weight 11000 with block random addition of oxyethylene units and oxypropylene units at molar ratio of 40/60.
       (P-3): Octoxy polyalkylene glycol ether with average molecular weight 1000 with random addition of oxyethylene units and oxypropylene units at molar ratio of 50/50.
       (P-4): Methoxy polyalkylene glycol ether with average molecular weight 12000 with random addition of oxyethylene units and oxypropylene units at molar ratio of 25/75.
       (MS-1)-(MS-4) and (PS-1)-(PS-7) are each straight-chain polyether modified polyorganosiloxane shown by Formula (1) and as explained in Table 3 wherein "B" indicates "block addition" and "R" indicates "random addition".
       (QS-1)-(QS-5) are each quaternary onium salt shown by Formula (2) and as explained in Table 4.
       (FN-1): Sodium isostearate.
       (PA-1): Dibutylethanol amine salt of decyloxy polyethoxy (n=4) ethylphosphate.
       (ES-1): Octyl laurate
       (EE-1): Ester of octyloxypolyethoxylate (number of ethoxy units n = 5) and lauric acid
       (EE-2): Ester of octyloxypolyalkoxylate (polyalkoxylate being random connection of 5 ethoxy units and 3 propoxy units) and lauric acid.
       (cr-1): Linear polydimethylsiloxane with average molecular weight 3000.
       (cr-2): Linear polyorganosiloxane with 2 methyl-phenyl siloxane units and 20 dimethylsiloxane units connected linearly.
       (cr-3): Pendant-type polyether modified polyorganosiloxane with 140 dimethyl siloxane units and 8 siloxane units having polyether groups randomly connected linearly by siloxane-bonding, the polyether groups each consisting of random connection of 80 oxyethylene units and 20 oxypropylene units.
       (cr-4): Pendant-type polyether modified polyorganosiloxane with average molecular weight 8600, having dimethylsiloxane units and siloxane units with polyether groups randomly connected linearly by siloxane-bonding, polyether groups contained by 92 weight %, the polyether groups each consisting of random connection of 15 oxyethylene units and 15 oxypropylene units.
    Part inside [ ]
    Siloxane unit
    R1 A1O p B/R R2 R5 m R3 OA2 q B/R n R4
    MS-1 OO EO 10 B TM M 5 TM OE 10 B 1 LR
    MS-2 OO EO/PO =10/10 35 B TM M 10 TM OE/OP =10/10 35 B 1 OO
    MS-3 PH EO/PO =10/10 20 B TM M 17 TM OE/OP =10/10 20 B 1 PP
    MS-4 OL EO/PO =15/5 20 R TM M/γ =23/2 25 TM OE/OP =15/5 20 R 1 OL
    PS-1 BO EO/PO =30/30 60 B TEM M 10 TEM OE/OP =30/30 60 B 2 BO
    PS-2 AO EO/PO =15/45 60 R TM M 10 TM OE/OP =15/45 60 R 2 AO
    PS-3 BU EO/PO =80/20 100 R TEM M 10 TEM OE/OP =80/20 100 R 7 BU
    PS-4 AO EO/PO =125/25 150 B TM M 50 TM OE/OP =125/25 150 B 15 AO
    PS-5 AO EO/PO =80/100 180 B TM M 180 TM OE/OP =80/100 180 B 30 AO
    PS-6 DB EO/PO =10/10 20 B TEM M/F =10/5 15 TEM OE/OP =10/10 20 B 2 DE
    PS-7 OT EO/PO =10/10 20 B TEM M 30 TEM OE/OP =10/10 20 B 4 OT
    In Table 3:
       OO: Octyloxy group
       PH: Phenoxy group
       OL: Oleoyl group
       BO: Butoxy group
       AO: Allyloxy group
       BU: Butenyloxy group
       DB: Dibutylamino group
       OT: Octylthio group
       EO: Ethoxy group
       PO: Propoxy group
       B/R: Block addition (B) or random addition (R)
       TM: Trimethylene group
       TEM: Tetramethylene group
       M: Methyl group
       γ: γ-trifluoropropyl group
       F: Phenyl group
       OE: Oxyethylene group
       OP: Oxypropylene group
       LR: Lauroyl group
       PP: Propyl phenoxy group
       DE: Dibutylethanol amino group
    X R6 R7 R8 R9 Compound which forms B y
    QS-1 N BT BT BT M Oleic acid 1
    QS-2 N M M M OC Lauryl sulfonate 1
    QS-3 N HOE HOE M OY Pentadecenyl succinic acid 2
    QS-4 P BT BT BT M Tridecyl sulfonate 1
    QS-5 P BT BT BT BT Isostearic acid 1
    QS-6 N BT BT BT M Octylphenylethoxy ethylsulfate 1
    In Table 4:
       BT: Butyl group
       M: Methyl group
       HOE: Hydroxyethyl group
       OC: Octyl group
       OY: Oleyl group
  • Part 2 (Application to partially drawn polyester filament yarns)
  • Water was added to the agents prepared in Part 1 to obtain aqueous emulsions with concentration of agent 15%. After polyethylene terephthalate chips with intrinsic viscosity 0.64 and containing titanium oxide by 0.2% were dried by a usual method, an extruder was used for spinning at 295°C. The aqueous emulsions were applied by a roller oiling method to the traveling yarns after they were extruded from the spinneret and cooled to be hardened. They were wound up at the speed of 3300m/minute without mechanical drawing to obtain wound 10kg cakes of partially drawn 150-denier, 72-filament yarns with agents adhered at ratios shown in Tables 5 and 6.
  • These cakes were used to carry out false twisting by a continuous operation for 25 days of a contact heater type false twisting apparatus described below and the contamination of heater was evaluated. The results are shown in Tables 5 and 6.
  • Apparatus: SDS1200B by Ernest Skrag and Sons, Inc.
  • Processing speed: 800m/minute
  • Draw ratio: 1.522
  • Twisting system: Three-axis disk friction method (with one guide disk on entrance side, one guide disk on exit side and seven hard polyurethane disks)
  • Heater on twist side: Length = 2.5m and surface temperature = 212°C
  • Heater on untwisting side: None
  • Intended number of twisting: 3300T/m
  • After the 25-day continuous operation of the apparatus, the heater tar on the yarn path on the surface of the heater on the twist side was removed by a brush, collected and weighed. The weights were measured for ten spindles, and the results are shown as the average weight (mg) per spindle.
  • The cakes were also used to carry out false twisting by a continuous operation for 33 days of a short heater type false twisting apparatus described below and the contamination of heater ( or "heater deposits") was evaluated. The results are also shown in Tables 5 and 6.
  • Apparatus: No. 33J Mach Crimper by Murata Kikai, Inc.
  • Processing speed: 900m/minute
  • Draw ratio: 1.522
  • Twisting system: Nip belt friction method
  • Heater on twist side: Length = 1m (with entrance part = 30cm and exit part = 70cm) and surface temperature = 480°C at entrance part and 410°C at exit part)
  • Heater on untwisting side: None
  • Intended number of twisting: 3300T/m
  • After the 33-day continuous operation of the apparatus, the sludge which became attached to the surface of the ceramic yarn path controlling guide was removed by a brush, collected and weighed. The results are shown as explained above for the case of the contact heater type.
    Test Example No. Agent used Adhesion ratio (%) Evaluation of heater contamination
    Contact heater (mg) Short heater (mg)
    20 Test Example 1 0.4 98 23
    21 Test Example 2 0.4 84 18
    22 Test Example 3 0.4 79 15
    23 Test Example 4 0.4 79 16
    24 Test Example 5 0.4 60 6
    25 Test Example 6 0.4 75 10
    26 Test Example 7 0.4 82 17
    27 Test Example 8 0.4 140 35
    28 Test Example 9 0.4 155 38
    29 Test Example 10 0.8 85 18
    30 Test Example 11 0.4 205 65
    31 Test Example 12 0.4 210 60
    32 Test Example 13 0.4 220 70
    33 Test Example 14 0.3 160 28
    34 Test Example 15 0.3 155 30
    35 Test Example 16 0.3 150 26
    36 Test Example 17 0.3 170 45
    37 Test Example 18 0.3 95 24
    38 Test Example 19 0.3 68 13
    Comparison Example No. Agent used Adhesion ratio (%) Evaluation of heater contamination
    Contact heater (mg) Short heater (mg)
    17 Comparison Example 1 0.4 540 190
    18 Comparison Example 2 0.4 510 180
    19 Comparison Example 3 0.4 500 205
    20 Comparison Example 4 0.4 555 185
    21 Comparison Example 5 0.4 1150 420
    22 Comparison Example 6 0.4 1030 395
    23 Comparison Example 7 0.4 670 310
    24 Comparison Example 8 0.4 705 340
    25 Comparison Example 9 0.4 580 305
    26 Comparison Example 10 0.4 1500 180
    27 Comparison Example 11 0.4 1200 445
    28 0.4
    In Tables 5 and 6:
    Adhesion ratio: Amount (in %) of agent which became adhered to partially drawn yarn of polyester
  • Part 3 (Application to partially drawn nylon filament yarns)
  • Water was added to the agents prepared in Part 1 to obtain aqueous emulsions with concentration of agent 10%. After nylon-6,6 chips with sulfuric acid relative viscosity 2.4 containing titanium oxide by 0.1% were dried by a usual method, an extruder was used for spinning at 290°C. The aqueous emulsions were applied by a guide oiling method to the traveling yarns after they were extruded from the spinneret and cooled to be hardened. They were wound up at the speed of 4000m/minute without mechanical drawing to obtain wound 8kg cakes of partially drawn 70-denier, 24-filament yarns with agents adhered at ratios shown in Table 7.
  • The cakes thus obtained were used to carry out false twisting under the same conditions as in Part 2 except the following, and the contamination of the heater was evaluated also as done in Part 2.
  • Conditions for false twisting by a contact heater type false twisting apparatus:
  • Draw ratio: 1.220
  • Twisting system: Three-axis disk friction method (with one guide disk on entrance side, one guide disk on exit side and five ceramic disks)
  • Intended number of twisting: 3000T/m
  • Conditions for false twisting by a short heat type false twisting apparatus:
  • Processing speed: 1000m/minute
  • Draw ratio: 1.220
  • Heater on twist side: Surface temperature = 475°C at entrance part and 380°C at exit part)
  • Intended number of twisting: 3000T/m.
  • Example No. Agent used Adhesion ratio (%) Evaluation of heater contamination
    Contact heater (mg) Short heater (mg)
    Test Examples
    39 Test Example 3 0.50 85 25
    40 Test Example 4 0.55 87 28
    41 Test Example 5 0.45 75 19
    42 Test Example 10 0.65 88 30
    43 Test Example 11 0.55 228 70
    Comparison Examples
    29 Comparison Example 10 0.55 1450 200
    30 Comparison Example 11 0.55 1230 390
    31 Comparison Example 12 0.55 1080 405
    32 Comparison Example 13 0.55 760 305
    33 Comparison Example 14 0.55 595 300
    34 Comparison Example 15 0.55
    35 Comparison Example 16 0.55 1280 250
    In Table 7:
    Adhesion ratio: Amount (in %) of agent which became adhered to partially drawn yarns of polyester filaments.
  • Part 4 (Application to directly spun drawn polyester filament yarns)
  • Water was added to the agents prepared in Part 1 to obtain aqueous emulsions with concentration of agent 10%. The emulsions were applied to the running yarns of polyester filaments by the guide oiling method and the yarns were wound up by means of a first godet roller rotating at the rate of 3000m/minute, drawn mechanically between the second godet roller and wound up at the rate of 5000m/minute to obtain wound 5kg cakes of 75-denier, 36-filament directly spun drawn yarns with agents adhered at ratio of 0.35% with respect to the yarns.
  • The cakes thus obtained were used to carry out false twisting under the same conditions as in Part 2 except the overfeed ratio was 3% and the speed of false twisting process was 650m/minute, and the contamination of the heater was evaluated also as done in Part 2. The results of evaluation are shown in Fig. 8.
    Example No. Agent used Evaluation of heater contamination
    Contact heater (mg) Short heater (mg)
    Test Examples
    44 Test Example 3 75 18
    45 Test Example 5 60 15
    46 Test Example 8 125 33
    47 Test Example 12 225 58
    Comparison Examples
    36 Comparison Example 5 880 440
    37 Comparison Example 7 665 380
    38 Comparison Example 9 585 340
  • It should be clear from the above that agents and methods according to the present invention are capable of sufficiently prevent the contamination of heaters for processing synthetic fibers even if the process is for false twisting including a severe heat treatment.

Claims (11)

  1. An agent for processing synthetic fibers, said agent comprising a polyether compound, a straight-chain polyether modified polyorganosiloxane shown by Formula (1) given below and ionic surfactant, said agent containing said straight-chain polyether modified polyorganosiloxane at a level of 0.1-12 weight % and said ionic surfactant at a level of 0.1-12 weight %, said Formula (1) being:
    Figure 00340001
    where R1 and R4 are each either a residual group obtained by removing active hydrogen from a monohydric compound containing active hydrogen and having 1-40 carbon atoms or hydroxyl group; R2 and R3 are each an alkylene group with 3 or 4 carbon atoms, R5 is an alkyl group with 1-4 carbon atoms, a fluoroalkyl group with 1-4 carbon atoms or a phenyl group, A1 and A2 are each an alkylene group with 2-4 carbon atoms, p and q are each an integer from 2-200, m is an integer from 3-200 and n is an integer from 1-30.
  2. The agent of claim 1 wherein R1 and R4 are each either an alkoxy group with 1-10 carbon atoms or an alkenoxy group with 2-10 carbon atoms, R5 is a methyl group, A1 and A2 are each alkylene groups with 2 or 3 carbon atoms, p and q are each an integer from 20-150, m is an integer from 5-20, and n is an integer from 1-9.
  3. The agent of claim 1 wherein said ionic surfactant is quaternary onium salt given by:
    Figure 00350001
    where X is N or P, R6, R7, R8 and R9 are each an alkyl group with 1-25 carbon atoms, an alkenyl group with 2-25 carbon atoms or a hydroxyalkyl group with 1-6 carbon atoms, By- is anion group of valence y obtained by removing hydrogen ions from a compound selected from the group consisting of acidic phosphoric acid esters with 1-30 carbon atoms, acidic sulfuric acid esters with 1-30 carbon atoms, acidic sulfonic acid esters with 1-30 carbon atoms and carboxylic acids with 1-30 carbon atoms, and y is an integer from 1-3.
  4. The agent of claim 3 wherein By- is an anion group of valence y obtained by removing hydrogen ions from a compound selected from the group consisting of acidic aliphatic phosphoric acid esters with 1-26 carbon atoms, acidic aliphatic sulfonic acid esters with 1-26 carbon atoms and aliphatic carboxylic acids with 1-26 carbon atoms.
  5. The agent of claim 1 wherein said polyether compound has average molecular weight of 700-20000, having oxyethylene units and oxypropylene units as principal structural units.
  6. The agent of claim 4 wherein said polyether compound has average molecular weight of 700-20000, having oxyethylene units and oxypropylene units as principal structural units.
  7. The agent of claim 5 further containing 1-30 weight % of an ester compound and/or an ether ester compound with a total number of carbon atoms 10-50.
  8. The agent of claim 6 further containing 1-30 weight % of an ester compound and/or an ether ester compound with total number of carbon atoms 10-50.
  9. A method of processing synthetic fibers which are subjected to a heat treatment, said method comprising the step of applying an agent according to any of claims 1 to 8 to said synthetic fibers at a ratio of 0.1-3 weight % with respect to said synthetic fibers.
  10. The method of claim 9 further comprising the step of subjecting said synthetic fibers to a false twisting process.
  11. The method of claim 10 wherein said false twisting process is carried out by using a short heater operating at 300-600°C.
EP99303196A 1998-04-27 1999-04-26 Agents for and methods of processing synthetic fibers Expired - Lifetime EP0953673B1 (en)

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JP13457598A JP3907313B2 (en) 1998-04-27 1998-04-27 Treatment agent for synthetic fiber used in false twisting process and method for treating synthetic fiber

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JP4486804B2 (en) * 2003-11-20 2010-06-23 日本化薬株式会社 Cellulose fiber deep colorant, deep color method using the same, and cellulosic fiber dyed product processed thereby
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JP4456532B2 (en) * 2004-08-03 2010-04-28 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber treatment method
WO2012000189A1 (en) * 2010-06-30 2012-01-05 Dow Global Technologies Llc Branched secondary alcohol alkoxylate surfactants for textile processing
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JP6310168B1 (en) * 2018-01-09 2018-04-11 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber
JP6632016B1 (en) * 2019-07-05 2020-01-15 竹本油脂株式会社 Treatment agent for carbon fiber precursor, and carbon fiber precursor
CN114269984A (en) * 2019-08-20 2022-04-01 松本油脂制药株式会社 Treating agent for elastic fiber and use thereof
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JPH0192475A (en) * 1987-09-30 1989-04-11 Takemoto Oil & Fat Co Ltd Oil composition for treating synthetic fiber
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JPH11315480A (en) 1999-11-16
DE69900339T2 (en) 2002-07-04
EP0953673A2 (en) 1999-11-03
KR19990082689A (en) 1999-11-25
CN1233686A (en) 1999-11-03
TW559633B (en) 2003-11-01
CN1114006C (en) 2003-07-09

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