WO2014148368A1 - 弾性繊維用処理剤及び弾性繊維 - Google Patents
弾性繊維用処理剤及び弾性繊維 Download PDFInfo
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- WO2014148368A1 WO2014148368A1 PCT/JP2014/056834 JP2014056834W WO2014148368A1 WO 2014148368 A1 WO2014148368 A1 WO 2014148368A1 JP 2014056834 W JP2014056834 W JP 2014056834W WO 2014148368 A1 WO2014148368 A1 WO 2014148368A1
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6433—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing carboxylic groups
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Definitions
- the present invention relates to an elastic fiber treatment agent used when producing an elastic fiber and an elastic fiber to which the treatment agent is applied.
- the elastic fiber In the spinning process, the elastic fiber is wound into a cheese shape after applying a treatment agent, and becomes a stringed body (hereinafter sometimes referred to as cheese).
- the elastic fiber is a fiber that is easily stuck because it has viscoelasticity.
- the sticking progresses with time due to the pressure applied during winding. Therefore, when using an elastic fiber thread body, unwinding is poor and thread breakage is caused.
- various treatment agents for elastic fibers have been developed.
- Patent Document 1 describes a treatment agent for elastic fibers containing amino-modified silicone.
- Patent Document 2 describes an elastic fiber treatment agent containing carbinol-modified silicone (polysiloxane).
- Patent Document 3 describes an elastic fiber treatment agent containing at least one of polyether-modified silicone, carbinol-modified silicone, carboxyl-modified silicone, amino-modified silicone, mercapto-modified silicone, and fluorine-modified silicone.
- Patent Document 4 describes an elastic fiber treatment agent containing a silicone resin (MQ resin).
- Patent Document 5 describes a processing agent for elastic fibers containing a silicone resin and / or an organic phosphate ester salt.
- Elastic fiber has a unique property that the fiber itself expands and contracts. For this reason, when the fiber string is subjected to a post-processing step, the yarn is often drawn out at a speed higher than the feed-out speed and the filament is drawn.
- this stretching causes a loop phenomenon in which filaments located in the inner layer are drawn simultaneously with the filaments that should originally be drawn from the cheese, and thereby the yarn It may cause cutting. For this reason, there are cases in which workability in post-processing, deterioration in fabric quality, and the like are caused.
- An object of the present invention is to provide an elastic fiber treatment agent capable of imparting excellent unwinding properties to an elastic fiber and suppressing the occurrence of loops when the cheese of the elastic fiber is stretched, and the treatment agent. It is to provide elastic fibers.
- the present invention is an elastic fiber treatment agent containing at least one base component selected from silicone oil, mineral oil, and ester oil and a hydroxy acid having at least two carboxyl groups in the molecule. .
- the weight ratio of the base component in the entire treatment agent is preferably 60 to 99.9% by weight.
- the hydroxy acid is preferably a compound having 1 to 3 hydroxy groups in the molecule.
- the elastic fiber treating agent of the present invention preferably further contains a compound having an amino group.
- the amino group is preferably a primary amino group and / or a secondary amino group.
- the molar ratio (carboxyl group / amino group) between the carboxyl group of the hydroxy acid and the amino group of the compound having an amino group is preferably 20/1 to 1/20.
- the treating agent for elastic fibers of the present invention includes alkyl-modified silicone, ester-modified silicone, polyether-modified silicone, carbinol-modified silicone, epoxy-modified silicone, carboxy-modified silicone, mercapto-modified silicone, organopolysiloxane resin, and higher fatty acid metal salt. It is preferable to further contain at least one selected from
- the elastic fiber of the present invention is obtained by applying the above-mentioned elastic fiber treatment agent to a fiber main body.
- the treatment agent for elastic fiber of the present invention can impart excellent unwinding properties to the elastic fiber, and can suppress the occurrence of loops when the elastic fiber cheese is drawn. Since the elastic fiber of the present invention is provided with the elastic fiber treatment agent of the present invention, the elastic fiber has excellent unwinding properties, and the occurrence of loops is suppressed when the elastic fiber cheese is stretched.
- the schematic diagram explaining the measuring method of loop occurrence frequency The schematic diagram explaining the measuring method of unwinding speed ratio.
- This invention is a processing agent used when manufacturing an elastic fiber.
- the processing agent for elastic fibers of the present invention contains a base component and a specific hydroxy acid. Details will be described below.
- the base component is at least one selected from silicone oil, mineral oil, and ester oil.
- the silicone oil is not particularly limited, and examples thereof include polydimethylsiloxane, polyalkylsiloxane, and polyalkylphenylsiloxane. One or more silicone oils may be used.
- the viscosity of the silicone oil at 30 ° C. is preferably 2 to 100 mm 2 / s, more preferably 5 to 50 mm 2 / s, and still more preferably 5 to 20 mm 2 / s.
- the viscosity is lower than 2 mm 2 / s, the silicone oil may volatilize, and when it is higher than 100 mm 2 / s, the solubility of other components blended in the treatment agent may be deteriorated.
- the number average molecular weight of the silicone oil is preferably 400 or more, more preferably 600 to 4000, and still more preferably 700 to 3000.
- the amount of siloxane bonds (SiOR 2 R 3 : R 2 and R 3 each independently represents an organic group) in the silicone oil is preferably 10 to 55, more preferably 12 to 45, and more preferably 14 to 40 Further preferred.
- the organic groups of R 2 and R 3 are hydrocarbon groups having 1 to 24 carbon atoms, and are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, cyclohexane
- a propyl group, a cyclohexyl group, a phenyl group, a benzyl group and the like can be mentioned, and a methyl group and a phenyl group are particularly preferable.
- the mineral oil is not particularly limited, and examples thereof include machine oil, spindle oil, and liquid paraffin. Among these, as the mineral oil, liquid paraffin is preferable because the generation of odor is low. One or more mineral oils may be used.
- the viscosity of the mineral oil at 30 ° C. is preferably 30 to 350 seconds, more preferably 40 to 200 seconds, and still more preferably 50 to 100 seconds.
- the viscosity of the mineral oil is lower than 30 seconds, the quality of the obtained elastic fiber may be deteriorated.
- the viscosity of the mineral oil is higher than 350 seconds, the solubility of other components blended in the treatment agent may deteriorate.
- the ester oil is not particularly limited, but an ester of a carboxylic acid and an alcohol, more specifically, an ester of a monohydric alcohol and a monovalent carboxylic acid, an ester of a monohydric alcohol and a polyvalent carboxylic acid, or many And esters of monohydric alcohols and monovalent carboxylic acids.
- ester oils include esters produced from carboxylic acids and alcohols selected from the following, but esters that do not use the following carboxylic acids and alcohols as raw materials may also be used. 1 type (s) or 2 or more types may be used for ester oil.
- carboxylic acid here means the compound which does not have a hydroxyl group in a molecule
- the carboxylic acid is not particularly limited with respect to the number of carbon atoms, presence or absence of branching, valence, etc., and may be a higher fatty acid, a cyclic fatty acid, or a carboxylic acid containing an aromatic ring. good.
- Examples of monovalent carboxylic acids include valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, Examples include isostearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, lignoselenic acid, cetylonic acid, benzoic acid, and naphthalenecarboxylic acid.
- polyvalent carboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, phthalic acid, trimellitic acid, pyromellitic acid, and the like.
- Alcohol is not particularly limited in terms of its carbon number, presence or absence of branching, valence, etc., and may be a higher alcohol, a cyclic alcohol, or an alcohol containing an aromatic ring.
- monohydric alcohols include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, isotridecyl alcohol, myristyl alcohol, pentadecyl alcohol, 1-hexadecanol, palmi Trail alcohol, 1-heptadecanol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, nonadecyl alcohol, 1-eicosanol, behenyl alcohol, 1-tetracosanol, erucyl alcohol, lignoceryl alcohol, benzyl alcohol, 2 -Phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, phenol
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, butylene glycol, neopentyl glycol, 1,5-pentanediol, and 3-methyl. 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, etc. Is mentioned.
- ester oil examples include, but are not limited to, for example, heptyl valerate, heptyl caproate, octyl caproate, cetyl caprylate, isooctyl laurate, isopropyl myristate, isopropyl palmitate, isostearyl palmitate, stearin Butyl acrylate, octyl stearate, oleyl laurate, isotri-decyl stearate, octyl stearate, isooctyl stearate, tridecyl stearate, isobutyl stearate, methyl oleate, isobutyl oleate, heptyl oleate, oleyl oleate, dilaurin Polyethylene glycol acid, polyethylene glycol dimyristate, polyethylene glycol dioleate, polyethylene glycol distearate, polylaurate Lo
- the viscosity of the ester oil at 25 ° C. is preferably 5 mm 2 / s or more, more preferably 5 to 50 mm 2 / s, still more preferably 5 to 30 mm 2 / s. If the viscosity (25 ° C.) is less than 5 mm 2 / s, the yarn may swell, which is not preferable.
- the base component is smooth performance of silicone oil.
- silicone oil and mineral oil and / or ester oil it is preferable to use silicone oil and mineral oil in combination, and it is more preferable to use silicone oil and mineral oil in combination.
- the weight ratio (I / II) of the silicone oil (I) and the component (II) consisting of mineral oil and / or ester oil in the base component is preferably 30/70 to 95/5, and preferably 50/50 to 95/5 is more preferable.
- the weight ratio of the base component to the entire elastic fiber treatment agent is preferably 60 to 99.9% by weight, more preferably 70 to 99.8% from the viewpoint of maintaining fluidity when the treatment agent is used. %, More preferably 80 to 99.5% by weight, and most preferably 90 to 99% by weight.
- the elastic fiber treating agent of the present invention contains, in addition to the above base component, a hydroxy acid having at least two carboxyl groups in the molecule (hereinafter sometimes simply referred to as hydroxy acid).
- a hydroxy acid having one carboxyl group in the molecule is used, the desired effect cannot be obtained because the interaction with the yarn is small, and a useful effect due to the addition of the hydroxy acid is not expressed.
- One or two or more hydroxy acids may be used.
- the hydroxy acid is a compound having one or more hydroxy groups and two or more carboxyl groups in the molecule, there are no particular restrictions on the number of carbon atoms, the presence or absence of branching, the valence, etc. From the viewpoint of obtaining a useful effect, the following is preferable.
- the number of carbon atoms of the hydroxy acid is preferably 3 to 20, more preferably 3 to 15, and further preferably 3 to 10.
- the number of carboxyl groups of the hydroxy acid is preferably 2 to 10, more preferably 2 to 8, and further preferably 2 to 5.
- the number of hydroxy groups in the hydroxy acid is preferably from 1 to 10, from the viewpoint that if the number of hydroxy groups in the hydroxy acid is large, the hydrophilicity becomes too large and the stability in the base component may be lowered. More preferably, it is 1-5, and more preferably 1-3.
- hydroxy acid examples include hydroxymalonic acid, malic acid, tartaric acid, citric acid, isocitric acid, glucaric acid, galactaric acid, hydroxyphthalic acid, and hydroxyisophthalic acid.
- hydroxymalonic acid, malic acid, tartaric acid, citric acid, isocitric acid, hydroxyphthalic acid, and hydroxyisophthalic acid are preferable, and hydroxymalonic acid, malic acid, tartaric acid, citric acid, and hydroxyphthalic acid are more preferable.
- the state of the hydroxy acid in the treatment agent is not particularly limited, and may be dissolved in the system, dispersed as an individual, or partially dissolved and partially dispersed as an individual. Of course, it may be a salt with other components contained in the treatment agent.
- the weight ratio of the hydroxy acid in the entire elastic fiber treatment agent is not particularly limited, but is preferably 0.0001 to 15% by weight, more preferably 0.001 to 13% by weight, from the viewpoint of economy. More preferably, it is 0.01 to 10% by weight.
- the treatment agent for elastic fibers of the present invention preferably contains a compound having an amino group from the viewpoint that a hydroxy acid can be stably present in the base component.
- the compound which has an amino group may use 1 type (s) or 2 or more types.
- the amino group may be any of a primary amino group (—NH 2 ), a secondary amino group that is a mono-substituted amino group, and a tertiary amino group that is a di-substituted amino group.
- the compound having an amino group may have two or more amino groups in the molecule.
- the higher the proportion of hydrogen atoms bonded to nitrogen atoms replaced by carbon atoms the smaller the effect of allowing the hydroxy acid to exist stably.
- An amino group is preferred.
- Examples of the compound having an amino group include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, diethylamine, dioctylamine, distearylamine, methylstearylamine, polyoxypropylene-added laurylamine, polyoxyethylene-added laurylamine, polyoxy Examples include ethylene-added stearylamine, polyoxyethylene-added oleylamine, monoethanolamine, diethylethanolamine, laurylethanolamine, oleylpropylenediamine, trioctylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylstearylamine, and amino-modified silicone. .
- the structure of the amino-modified silicone is not particularly limited, and the amino-modified group having an amino group may be bonded to the side chain of the silicone that is the main chain, or may be bonded to the terminal, It may be combined with both. Further, the amino-modified group may be monoamine type or polyamine type, and both may coexist in one molecule of amino-modified silicone.
- the amine value of the amino-modified silicone is not particularly limited, but is preferably 0.1 to 200 (KOHmg / g), more preferably 0.5 to 150 (KOHmg / g), and particularly preferably 1 to 100 (KOHmg). / G), most preferably 1 to 50 (KOH mg / g).
- the amino-modified group is not particularly limited, and examples thereof include an aminopropyl group and an N- (2-aminoethyl) aminopropyl group. One or more amino-modified silicones may be used.
- the state of the compound having an amino group in the treatment agent is not particularly limited, and may be dissolved in the system, dispersed as an individual, or partially dissolved and partially dispersed as an individual. Or may form a salt with other components.
- the weight ratio of the amino group-containing compound in the entire elastic fiber treating agent is not particularly limited, but is preferably 0.0001 to 15% by weight, more preferably 0.001 to 13% by weight from the viewpoint of economy. Is more preferable, and 0.01 to 10% by weight is more preferable.
- the weight ratio of the hydroxy acid and the compound having an amino group (a compound having a hydroxy acid / amino group) from the viewpoint of further exerting the effects of the present invention. ) Is preferably 1/400 to 50/1, more preferably 1/200 to 30/1, and even more preferably 1/100 to 20/1.
- the treatment agent for elastic fibers of the present invention contains a compound having an amino group
- the amino group possessed by the compound having a carboxyl group and an amino group contained in the hydroxy acid in the treatment agent is more effective in the present invention.
- the molar ratio (carboxyl group / amino group) is preferably 20/1 to 1/20, more preferably 10/1 to 1/10, still more preferably 5/1 to 1/5.
- the treatment agent for elastic fibers of the present invention includes alkyl-modified silicone, ester-modified silicone, polyether-modified silicone, carbinol-modified silicone, epoxy-modified silicone, carboxy-modified silicone, mercapto-modified silicone, organo You may further contain at least 1 type of component (A) chosen from a polysiloxane resin and a higher fatty acid metal salt.
- a component (A) may use 1 type (s) or 2 or more types.
- the weight ratio of the component (A) in the entire elastic fiber treatment agent is preferably 0.01 to 15% by weight, more preferably 0.1 to 13% by weight, Preferably, it is 0.5 to 10% by weight.
- the modified silicone is generally a reactive (functional) group or a non-reactive group at least at one of both ends, one end, side chain, and both side chains of polysiloxane such as dimethyl silicone (polydimethylsiloxane) ( It has a structure in which at least one functional group is bonded.
- the modified silicone is an alkyl-modified silicone such as a modified silicone having a long-chain alkyl group (such as an alkyl group having 6 or more carbon atoms or a 2-phenylpropyl group); a modified silicone having an ester bond.
- a modified silicone having a long-chain alkyl group such as an alkyl group having 6 or more carbon atoms or a 2-phenylpropyl group
- a modified silicone having an ester bond such as an alkyl-modified silicone such as a modified silicone having a long-chain alkyl group (such as an alkyl group having 6 or more carbon atoms or a 2-phenylpropyl group); a modified silicone having an ester bond.
- Ester-modified silicones polyether-modified silicones that are modified silicones having polyoxyalkylene groups (for example, polyoxyethylene groups, polyoxypropylene groups, polyoxyethyleneoxypropylene groups, etc.); modified silicones having alcoholic hydroxyl groups Carbinol-modified silicone; epoxy-modified silicone that is a modified silicone having an epoxy group such as a glycidyl group or an alicyclic epoxy group; a carboxy-modified silicone that is a modified silicone having a carboxyl group; having a mercapto group Can be mentioned a mercapto-modified silicone is a modified silicone,
- An organopolysiloxane resin (hereinafter simply referred to as a silicone resin) means a silicone having a three-dimensional crosslinked structure.
- the silicone resin is generally at least one component selected from a monofunctional constituent unit (M), a bifunctional constituent unit (D), a trifunctional constituent unit (T), and a tetrafunctional constituent unit (Q). It consists of units.
- silicone resin examples include silicone resins such as MQ silicone resin, MQT silicone resin, T silicone resin, and DT silicone resin.
- R a R b R c SiO 1/2 that is a monofunctional structural unit (provided that R a, R b, and R c are all hydrocarbon groups) and tetrafunctional.
- a silicone resin containing SiO 4/2 which is a structural unit.
- Examples of the MQT silicone resin include R a R b R c SiO 1/2 that is a monofunctional structural unit (provided that R a , R b, and R c are all hydrocarbon groups) and a tetrafunctional group. And a silicone resin containing SiO 4/2 which is a structural unit and RSiO 3/2 which is a trifunctional structural unit (wherein R is a hydrocarbon group).
- T-silicone resin examples include a silicone resin containing RSiO 3/2 (where R is a hydrocarbon group) which is a trifunctional structural unit (the terminal of which is a hydrocarbon group, silanol group or alkoxy group). Or the like)).
- R a R b SiO 2/2 which is a bifunctional structural unit (wherein R a and R b are both hydrocarbon groups) and a trifunctional structural unit.
- R a and R b are both hydrocarbon groups
- RSiO 3/2 where R is a hydrocarbon group
- the hydrocarbon group for R, R a , R b and R c is a hydrocarbon group having 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, An isopentyl group, a hexyl group, a cyclopropyl group, a cyclohexyl group, a phenyl group, a benzyl group and the like can be mentioned, and a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a phenyl group are particularly preferable.
- higher fatty acid metal salts include divalent or trivalent metal salts of fatty acids having 8 to 22 carbon atoms.
- Examples of higher fatty acid metal salts include calcium laurate, calcium palmitate, barium myristate, magnesium palmitate, magnesium laurate, magnesium stearate, magnesium 2-ethylhexylate, zinc behenate, aluminum tribehenate, calcium stearate, 2 -Calcium ethylhexylate, aluminum stearate, aluminum palmitate, barium stearate, zinc caprate, zinc stearate and the like.
- the average particle size of the higher fatty acid metal salt is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 3 ⁇ m, and particularly preferably 0.05 to 2 ⁇ m.
- the average particle size of the higher fatty acid metal salt is less than 0.01 ⁇ m, the effect of addition may not be observed.
- the average particle size of the higher fatty acid metal salt is more than 5 ⁇ m, it may easily fall off from the fiber surface and may cause scum in the post-spinning process.
- the average particle size was measured using a batch cell of a particle size distribution measuring device (LA-910, manufactured by Horiba, Ltd.), setting the refractive index to 1.02, and measuring the volume-based average particle size.
- the shape of the higher fatty acid metal salt is not particularly limited, but a needle shape is preferable.
- the ratio between the vertical direction and the horizontal direction is preferably 10: 1 to 2: 1 and more preferably 8: 1 to 3: 1 from the viewpoint of unraveling property. .
- the elastic fiber treatment agent of the present invention may contain a surfactant such as a nonionic surfactant and an anionic surfactant as long as the effects of the present invention are not impaired.
- the weight ratio of the surfactant to the whole elastic fiber treatment agent is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and further preferably 0.5 to 10% by weight.
- Nonionic surfactants are not particularly limited, and examples thereof include polyoxyethylene alkyl ethers having 8 to 22 carbon atoms (EO 1 to 20 mol) and polyoxypropylene alkyls having 8 to 22 carbon atoms.
- Ether PO 1 to 20 mol
- sorbitan fatty acid ester EO 1 to 20 mol
- PO adduct of sorbitan fatty acid ester PO 1 to 20 mol
- Alkylphenol EO adduct of alkylphenol having 6 to 22 carbon atoms
- fatty acid polyoxyethylene glycol ester EO 1 to 20 mol
- fatty acid polyoxypropylene glycol ester PO 1 to 20 mol
- anionic surfactant examples include, but are not limited to, alkane sulfonic acid, dialkyl sulfosuccinic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl sulfuric acid, polyoxyethylene alkyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether. There are phosphoric acid or salts of these components.
- an alkanesulfonic acid having an alkyl group having 6 to 22 carbon atoms and / or an alkali metal salt thereof a dialkylsulfosuccinic acid having an alkyl group having 6 to 22 carbon atoms and / or an alkali metal salt thereof, Alkylbenzenesulfonic acid having an alkyl group of ⁇ 22 and / or alkali metal salt thereof, alkylsulfuric acid having an alkyl group of 1 to 20 carbon atoms and / or salt thereof, polyoxyethylene alkyl having an alkyl group of 6 to 22 carbon atoms Ether sulfuric acid and / or salt thereof, alkyl phosphoric acid having an alkyl group having 6 to 22 carbon atoms, alkali metal salt and / or alkaline earth metal salt of alkyl phosphoric acid having an alkyl group having 6 to 22 carbon atoms, carbon number Polyoxyethylene alkyl ether phosphoric acid having an alkyl group of 6 to 22,
- the treatment agent for elastic fibers of the present invention may contain components usually used as a treatment agent for elastic fibers such as a binder, an antistatic agent, an antioxidant, and an ultraviolet absorber.
- a binder an antistatic agent
- an antioxidant an antioxidant
- an ultraviolet absorber One or two or more components other than the base component, hydroxy acid, compound having an amino group and component (A) described above (hereinafter sometimes referred to as other components) may be used.
- the weight ratio of the other components in the entire elastic fiber treatment agent is preferably 0.01 to 15% by weight from the viewpoint of maintaining fluidity when using the treatment agent.
- the viscosity of the elastic fiber treating agent of the present invention at 30 ° C. is preferably 5 to 50 mm 2 / s, more preferably 5 to 20 mm 2 / s. If the viscosity is too low, when the elastic fiber is run in the spinning and post-processing steps, the treatment agent may scatter in the form of a mist, and the surroundings may be soiled or the operator may inhale. On the other hand, if the viscosity is too high, when the elastic fiber is run in the spinning and post-processing steps, the running roller may wind the yarn around the running roller due to adhesiveness, which may cause yarn breakage.
- the method for producing the treatment agent for elastic fiber of the present invention is not particularly limited, and a known method can be adopted. For example, a method in which some components are blended in advance and mixed with other components may be used, or a method in which all components are mixed at once. Further, when the treatment agent for elastic fibers of the present invention contains a higher fatty acid metal salt, it may be produced by mixing an already pulverized higher fatty acid metal salt with a base component or the like. May be mixed and pulverized to a predetermined average particle size using a conventionally known wet pulverizer such as a vertical bead mill, a horizontal bead mill, a colloid mill, a jet mill, or a sand grinder.
- a conventionally known wet pulverizer such as a vertical bead mill, a horizontal bead mill, a colloid mill, a jet mill, or a sand grinder.
- the elastic fiber of the present invention is obtained by applying the elastic fiber treatment agent of the present invention to an elastic fiber main body.
- the adhesion ratio of the elastic fiber treatment agent to the entire elastic fiber is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.
- the method for applying the elastic fiber treatment agent of the present invention to the elastic fiber body is not particularly limited, and a known method can be employed.
- the elastic fiber (elastic fiber body) of the present invention is a fiber having elasticity using polyether polyurethane, polyester polyurethane, polyether ester elastomer, polyester elastomer, polyethylene elastomer, polyamide elastomer, etc., and its elongation is usually 300% or more.
- the elastic fiber of the present invention is made of polyurethane or polyurethane urea obtained by reacting PTMG or polyester diol with an organic diisocyanate and then extending the chain with 1,4 butanediol, ethylenediamine, propylenediamine, pentanediamine or the like.
- a 20 to 40% solution of a polyurethane urea polymer obtained by reacting in a solvent such as acetamide or dimethylformamide and chain-extending with a diamine such as ethylenediamine or propanediamine is spin-spun at a spinning speed of 400 to 1200 m / min.
- a solvent such as acetamide or dimethylformamide
- a diamine such as ethylenediamine or propanediamine
- the adaptive fineness of the elastic fiber body is not particularly limited.
- the elastic fiber body of the present invention may contain inorganic substances such as titanium oxide, magnesium oxide, hydrotalcite, zinc oxide, and divalent metal soap.
- Divalent metal soaps include calcium 2-ethylhexylate, calcium stearate, calcium palmitate, magnesium stearate, magnesium palmitate, magnesium laurate, barium stearate, zinc caprate, zinc behenate, zinc stearate, etc. Can be mentioned. 1 type (s) or 2 or more types may be used for an inorganic substance.
- the uniform unwinding property may be poor, but the uniform unwinding property can be improved by applying the treatment agent of the present invention to the elastic fiber body. Therefore, the processing agent for elastic fibers of the present invention can be suitably used when the elastic fiber main body contains an inorganic substance.
- the content of inorganic substances in the elastic fiber body is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight.
- the elastic fiber of the present invention can be used as a cloth by processing yarn such as covering yarn such as CSY, single covering, PLY, air covering, circular knitting, tricot and the like.
- covering yarn such as CSY, single covering, PLY, air covering, circular knitting, tricot and the like.
- products that require elasticity such as stockings, socks, underwear and swimwear, and outerwear such as jeans and suits are given elasticity for comfort. Also used for purposes. More recently, it has been applied to disposable diapers.
- the loop evaluation was evaluated according to the following criteria. A: Less than 20 loops / min. ⁇ : Loop 20 times / minute or more and less than 50 times / minute (can be used without problems by adjusting the use conditions) ⁇ : Loop 50 times / minute or more and less than 80 times / minute (There is a possibility that thread breakage may occur due to the loop, and there is a problem in operability.) ⁇ : Loop 80 times / minute or more (Because a thread breakage occurs due to the occurrence of a loop, there is a very problem in operability.)
- the unraveling speed ratio was evaluated according to the following criteria.
- Examples 1 to 34 Comparative Examples 1 to 9
- a polytetramethylene ether glycol having an average molecular weight of 1600 is reacted with 4,4′-diphenylmethane diisocyanate in a molar ratio of 1: 2, and then chain-extended using a dimethylformamide solution of 1,2-diaminopropane to form a polymer as a spinning dope.
- a dimethylformamide solution having a concentration of 33% was obtained.
- the viscosity of the spinning dope was 1900 mPaS (measurement temperature: 30 ° C.).
- a-1 Liquid paraffin 40 seconds
- a-2 Liquid paraffin 60 seconds
- b-1 dimethyl silicone 10 mm2 / s
- b-2 dimethylsilicone 20 mm2 / s
- c-1 isopropyl myristate
- c-2 isostearyl palmitate
- d-1 malic acid
- d-2 hydroxymalonic acid
- d-3 citric acid
- d-4 tartaric acid.
- e-1 38.6% by weight of malic acid and 61.4% by weight of myristylamine mixed.
- e-2 4.3% by weight of hydroxyfumaric acid and 95.7% by weight of oleylamine mixed together.
- e-3 A mixture of citric acid at 42.1% by weight and oleylamine at 57.9% by weight.
- e-4 92.1% by weight of tartaric acid and 7.9% by weight of myristylamine mixed.
- e-5 36.4% by weight of hydroxyfumaric acid and 63.6% by weight of diethanolamine mixed together.
- e-6 37.0 wt% malic acid and 63.0 wt% laurylethanolamine mixed.
- e-7 0.3% by weight of citric acid and 99.7% by weight of amino-modified silicone I mixed.
- e-8 74.4% by weight of tartaric acid and 25.6% by weight of dibutylamine mixed together.
- e-9 6.1% by weight of hydroxyfumaric acid and 93.9% by weight of laurylamine mixed together.
- e-10 10.9% by weight of citric acid and 89.1% by weight of diethanolamine mixed.
- e-11 A mixture containing 9.0% by weight of hydroxyfumaric acid and 91.0% by weight of amino-modified silicone II.
- e-12 A mixture obtained by mixing 97.0% by weight of tartaric acid and 3.0% by weight of laurylethanolamine.
- e-13 A mixture of malic acid at 4.0% by weight and oleylpropylenediamine at 96.0% by weight.
- e-14 40.9 wt% citric acid and 59.1 wt% laurylamine mixed.
- e-15 A mixture of 9.4% by weight of malic acid and 90.6% by weight of dibutylamine.
- e-16 18.8% by weight of tartaric acid and 81.2% by weight of oleylpropylenediamine mixed.
- e-17 A mixture of malic acid at 20.1% by weight and oleylamine at 79.9% by weight.
- e-18 1.1% by weight of citric acid and 98.9% by weight of amino-modified silicone III mixed.
- e-19 28.9% by weight of tartaric acid and 71.1% by weight of laurylamine mixed.
- e-20 15.4 wt% citric acid and 84.6 wt% dilaurylamine mixed.
- e-21 A mixture of malic acid at 16.0% by weight and dilaurylamine at 84.0% by weight.
- f-1 alkyl-modified silicone
- f-2 carbinol-modified silicone
- f-3 polyether-modified silicone
- f-4 organopolysiloxane resin
- f-5 calcium laurate
- f-6 magnesium stearate
- g-1 malonic acid
- g-2 trimellitic acid
- g-3 lactic acid
- g-4 isostearic acid
- h-1 A mixture containing 6.1% by weight of malonic acid and 93.9% by weight of oleylamine.
- h-2 Trimellitic acid 30.6 wt% and oleylamine 69.4 wt% mixed
- h-3 A mixture of 36.4% by weight of lactic acid and 63.6% by weight of diethanolamine.
- h-4 93.0% by weight of isostearic acid and 6.9% by weight of diethanolamine mixed.
- modified silicone and the organopolysiloxane resin are as follows.
- Amino-modified silicone I Side chain amino-modified, amine value 37 KOH mg / g, 800 mm 2 / s (25 ° C.).
- Amino-modified silicone II side chain amino-modified type, amine value 1 KOH mg / g, 15000 mm 2 / s (25 ° C.).
- Amino-modified silicone III Side chain amino-modified type, amine value 10 KOH mg / g, 100 mm 2 / s (25 ° C.).
- Alkyl-modified silicone Side chain alkyl-modified type, 25 mm 2 / s (25 ° C.).
- Carbinol-modified silicone side chain carbinol-modified type, hydroxyl value 62 KOH mg / g, 45 mm 2 / s (25 ° C.).
- Polyether-modified silicone side chain polyether-modified type, 100 mm 2 / s (25 ° C.).
- Organopolysiloxane resin MQ silicone resin type, 400 mm 2 / s (25 ° C.).
- the treatment agent of the present invention is suitably used when producing elastic fibers.
- the elastic fiber of the present invention is used for products that require stretchability.
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Abstract
Description
前記ヒドロキシ酸は、分子内に1~3個のヒドロキシ基を有する化合物であることが好ましい。
前記アミノ基は、1級アミノ基及び/又は2級アミノ基であることが好ましい。
前記ヒドロキシ酸が有するカルボキシル基と前記アミノ基を有する化合物が有するアミノ基とのモル比(カルボキシル基/アミノ基)は、20/1~1/20であることが好ましい。
本発明は、弾性繊維を製造する際に用いられる処理剤である。本発明の弾性繊維用処理剤は、ベース成分と特定のヒドロキシ酸を含有するものである。以下、詳細に説明する。
シリコーン油としては、特に限定はないが、たとえば、ポリジメチルシロキサン、ポリアルキルシロキサン、ポリアルキルフェニルシロキサン等を挙げることができる。シリコーン油は、1種又は2種以上を使用してもよい。
本発明の弾性繊維は、弾性繊維本体に、本発明の弾性繊維用処理剤が付与されたものである。弾性繊維全体に占める弾性繊維用処理剤の付着割合は0.1~15重量%が好ましく、0.5~10重量%がさらに好ましい。弾性繊維本体に本発明の弾性繊維用処理剤を付与する方法としては、特に限定はなく、公知の方法を採用できる。
図1において、解舒速度比測定機の解舒側に処理剤を付与した繊維のチーズ(1)をセットし、巻き取り側紙管(2)をセットする。解舒速度比を、解舒速度/巻取速度=1/4の一定速度にセットした後、ローラー(3)及び(4)を同時に起動させる。この状態で糸が4倍の状態で引き延ばされながら解舒していることとなる。この状態でチーズ(1)から解舒される糸(5)の状態を確認する。ループの発生するチーズでは解舒されている糸よりも内層側に位置する糸が、解舒される糸(5)につられて引き出され、ループ(6)となって確認される。このループ(6)の発生頻度を測定する。
◎:ループ20回/分未満(実際の後加工においてループ発生による糸切れ問題がなく、良好である。)
○:ループ20回/分以上、50回/分未満(使用条件の調整により問題なく使用できる。)
△:ループ50回/分以上、80回/分未満(ループによる糸切れ発生の可能性があり、操業性に問題がある。)
×:ループ 80回/分以上(ループの発生により糸切れが発生する為、操業性に非常に問題がある。)
図2において、解舒速度比測定機の解舒側に処理剤を付与した繊維のチーズ(7)をセットし、巻き取り側紙管(8)をセットする。巻取速度を一定速度にセットした後、ローラー(9)及び(10)を同時に起動させる。この状態では糸(11)に張力はほとんどかからないため、糸はチーズ上で膠着して離れないため解舒点(12)は図2に示す状態にある。解舒速度を変えることによって、チーズからの糸(11)の解舒点(12)が変わるので、この点がチーズとローラーとの接点(13)と一致するように解舒速度を設定する。解舒速度比は下記式(1)によって求める。この値が小さいほど、解舒性が良いことを示す。
解舒速度比(%)=((巻取速度-解舒速度)/解舒速度)×100 (1)
◎:解舒性100%未満(安定に解舒ができ、非常に良好である。)
○:解舒性100%以上120%未満(使用条件の調整により問題無く使用できる。)
△:解舒性120%以上150%未満(糸切れ等の発生がややあり、操業性に問題がある。)
×:解舒性150%以上(膠着により糸切れ等が多発し、操業性に非常に問題がある。)
平均分子量1600のポリテトラメチレンエーテルグリコールと、4,4‘-ジフェニルメタンジイソシアネートをモル比率1:2で反応させ、次いで1,2-ジアミノプロパンのジメチルホルムアミド溶液を用いて鎖延長し、紡糸原液としてポリマー濃度33%のジメチルホルムアミド溶液を得た。なお、紡糸原液の粘度は1900mPaS(測定温度:30℃)であった。
得られた紡糸原液を4つの細孔を有する紡糸口金より195℃のN2気流中に吐出して乾式紡糸した。弾性繊維用処理剤をそれぞれオイリングローラーで、紡糸中の走行糸(弾性繊維本体)に対して6重量%付与した。従って、弾性繊維全体に対して弾性繊維用処理剤が5.66重量%付与された。その後、弾性繊維用処理剤で処理した弾性繊維をそれぞれ毎分500mの速度でボビンに巻取り、77dtexモノフィラメントチーズ(巻き量400g)を得た。得られたチーズを用いて、上記評価方法によりそれぞれ評価した。その結果を表6、7に示す。
a-1:流動パラフィン 40秒、a-2:流動パラフィン 60秒。
b-1:ジメチルシリコーン 10mm2/s、b-2:ジメチルシリコーン 20mm2/s。
c-1:ミリスチン酸イソプロピル、c-2:パルミチン酸イソステアリル。
d-1:リンゴ酸、d-2:ヒドロキシマロン酸、d-3:クエン酸、d-4:酒石酸。
e-17:リンゴ酸を20.1重量%とオレイルアミンを79.9重量%とし、混合したもの。
e-18:クエン酸を1.1重量%とアミノ変性シリコーンIIIを98.9重量%とし、混合したもの。
e-19:酒石酸を28.9重量%とラウリルアミンを71.1重量%とし、混合したもの。
e-20:クエン酸を15.4重量%とジラウリルアミンを84.6重量%とし、混合したもの。
e-21:リンゴ酸を16.0重量%とジラウリルアミンを84.0重量%とし、混合したもの。
g-1:マロン酸、g-2:トリメリット酸、g-3:乳酸、g-4:イソステアリン酸。
h-1:マロン酸を6.1重量%とオレイルアミンを93.9重量%とし、混合したもの。h-2:トリメリット酸を30.6重量%とオレイルアミンを69.4重量%とし、混合したもの。h-3:乳酸を36.4重量%とジエタノールアミンを63.6重量%とし、混合したもの。h-4:イソステアリン酸を93.0重量%とジエタノールアミンを6.9重量%とし、混合したもの。
アミノ変性シリコーンI:側鎖アミノ変性型、アミン価37KOHmg/g、800mm2/s(25℃)。アミノ変性シリコーンII:側鎖アミノ変性型、アミン価1KOHmg/g、15000mm2/s(25℃)。アミノ変性シリコーンIII:側鎖アミノ変性型、アミン価10KOHmg/g、100mm2/s(25℃)。アルキル変性シリコーン:側鎖アルキル変性型、25mm2/s(25℃)。カルビノール変性シリコーン:側鎖カルビノール変性型、水酸基価62KOHmg/g、45mm2/s(25℃)。ポリエーテル変性シリコーン:側鎖ポリエーテル変性型、100mm2/s(25℃)。オルガノポリシロキサン樹脂:MQシリコーンレジン型、400mm2/s(25℃)。
2 巻き取り用紙管
3 ローラー
4 ローラー
5 走行糸条
6 ループ
7 チーズ
8 巻き取り用紙管
9 ローラー
10 ローラー
11 走行糸条
12 解舒点
13 チーズとローラーの接点
Claims (8)
- シリコーン油、鉱物油及びエステル油から選ばれる少なくとも1種のベース成分と、分子内に少なくとも2個のカルボキシル基を有するヒドロキシ酸とを含有する、弾性繊維用処理剤。
- 処理剤全体に占める前記ベース成分の重量割合が、60~99.9重量%である、請求項1に記載の弾性繊維用処理剤。
- 前記ヒドロキシ酸が、分子内に1~3個のヒドロキシ基を有する化合物である、請求項1又は2に弾性繊維用処理剤。
- アミノ基を有する化合物をさらに含有する、請求項1~3のいずれかに記載の弾性繊維用処理剤。
- 前記アミノ基が、1級アミノ基及び/又は2級アミノ基である、請求項4に記載の弾性繊維用処理剤。
- 前記ヒドロキシ酸が有するカルボキシル基と前記アミノ基を有する化合物が有するアミノ基とのモル比(カルボキシル基/アミノ基)が20/1~1/20である、請求項4又は5に記載の弾性繊維用処理剤。
- アルキル変性シリコーン、エステル変性シリコーン、ポリエーテル変性シリコーン、カルビノール変性シリコーン、エポキシ変性シリコーン、カルボキシ変性シリコーン、メルカプト変性シリコーン、オルガノポリシロキサン樹脂及び高級脂肪酸金属塩から選ばれる少なくとも一種をさらに含有する、請求項1~6のいずれかに記載の弾性繊維用処理剤。
- 弾性繊維本体に、請求項1~7のいずれに記載されている弾性繊維用処理剤が付与された、弾性繊維。
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WO2020130002A1 (ja) * | 2018-12-21 | 2020-06-25 | 日華化学株式会社 | 撥水剤組成物、及び撥水性繊維製品の製造方法 |
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JP5936292B1 (ja) * | 2015-05-11 | 2016-06-22 | 竹本油脂株式会社 | 乾式紡糸ポリウレタン系弾性繊維 |
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KR102137274B1 (ko) * | 2019-01-07 | 2020-07-23 | (주) 정산인터내셔널 | 우수한 해사성, 제직성 및 원사 수축율 특성을 가지는 열가소성 탄성체 원사 및 이의 제조방법 |
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