EP2653605B1 - Agent de traitement pour structure fibre polyester et procédé de fabrication de structure fibre polyester qui utilise ledit agent - Google Patents

Agent de traitement pour structure fibre polyester et procédé de fabrication de structure fibre polyester qui utilise ledit agent Download PDF

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Publication number
EP2653605B1
EP2653605B1 EP11847941.9A EP11847941A EP2653605B1 EP 2653605 B1 EP2653605 B1 EP 2653605B1 EP 11847941 A EP11847941 A EP 11847941A EP 2653605 B1 EP2653605 B1 EP 2653605B1
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Prior art keywords
finishing agent
terminal blocking
polyester
agent
treatment
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EP11847941.9A
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German (de)
English (en)
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EP2653605A1 (fr
EP2653605A4 (fr
Inventor
Masaru Harada
Keiji Takeda
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Toray Industries Inc
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Toray Industries Inc
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/1845—Aromatic mono- or polycarboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Definitions

  • the present invention is related to a finishing agent for a polyester-based fiber structure and a method of producing the polyester-based fiber structure using the finishing agent.
  • Polylactic acids have particularly drawn attention as biodegradable plastics made of natural resources. Because lactic acid which is a raw material of the polylactic acid can be obtained from plants such as corn, it can be said that the polylactic acid is an environment-conscious plastic. However, the polylactic acid has a property of being very highly hydrolysable in water at room temperature and high temperature, and can also be degraded even by the water in air, which limits environment and application where it is used.
  • protons released from the terminal carboxyl group act as a self catalyst and promote break down of esters, which is a common problem not only in the polylactic acid but also polyester-based fibers.
  • polyethylene terephthalate which is general-purpose polyester has a lower hydrolysis rate as compared with polylactic acid, it has sufficient hydrolysis-resistant properties when used for application in general clothing materials.
  • uniforms used in the field of medical treatment, nursing care, food product or the like require washing in a hot water bath at 60 to 90°C or autoclaving treatment at 120°C to 130°C, there is concern on deterioration of the fabric by such treatment. Due to this, in practice, the number of years of the uniforms in the field of medical treatment being used is relatively short and disposable uniforms account for high percentage.
  • Japanese Patent Application Laid-Open Publication No. 2001-261797 and Japanese Patent Application Laid-Open Publication No. 2002-30208 disclose methods of lowering the concentration of terminal carboxyl group by adding a terminal blocking agent.
  • these methods have a problem in that, because the terminal blocking agent is added to and kneaded with polymer chips before spinning, the terminal blocking agent causes fuming due to evaporation and decomposition to generate an offensive odor and toxic gas. Because of this, there is also a problem in that the terminal blocking agent must be excessively added. Further, fiber spinning properties become deteriorated and productivity becomes lower as well.
  • use of an inorganic substance as the terminal blocking agent can solve the problem of the poisonous gas at the time of the kneading and spinning. Yet, because it is a terminal blocking treatment in a fiber spinning stage, there is concern that the type of yarns is difficult to be changed and hydrolysis occurs in a process such as a dyeing step or post-processing step.
  • JP 2009-249450 discloses a method comprising dissolving a terminal blocking agent with a solvent or emulsifying the agent with an emulsifier and bringing the resultant into direct contact with processed material to add terminal blocking onto the surface of the processed material.
  • the terminal blocking agent is present only near the surface of a treated material in this method, the amount of terminal blocking agent added is not adequate and thus the hydrolysis-resistant property against heat and humidity for a long period of time is insufficient.
  • JP 2009-263840 discloses a method comprising adding a terminal blocking agent near the surface of a structure at a high concentration and adding the terminal blocking agent also to the inside of structure at a concentration equal to or higher than a certain concentration.
  • efficiency in taking up a terminal blocking agent into a treated product is low, resulting in high concentration of the terminal blocking agent used and high costs involved in it.
  • JP 2001-98459 discloses a method comprising, when a polyester fiber is treated with a treatment solution containing a fiber function imparting agent, letting a carrier coexist in the treatment solution. Yet, examples of a function finishing agent only include water repellent, water absorbent and flame retardant. There is no mention of effects of the carrier on a terminal blocking agent according to the invention. The effects are not concretely examined either.
  • JP 2000-226765 discloses a method comprising taking up a polymerization initiator using a phthalimide compound in a bath to carry out graft processing. Yet, there is no mention of effects of the phthalimide compound on the terminal blocking agent according to the invention. The effects are not concretely examined either.
  • the present invention was made in view of such conventional backgrounds, and an object thereof is to provide a finishing agent for a polyester-based fiber structure allowing a treated product to efficiently take up a carbodiimide compound and a method of producing the polyester-based fiber structure with excellent hydrolysis-resistant properties using the finishing agent.
  • the present invention comprises the following in order to achieve the above object.
  • a carbodiimide compound can be efficiently given to the surface and inside of a fiber structure containing a polyester-based fiber to render a high hydrolysis-resistant property.
  • treatment with a treatment solution in which, in conjunction with a carbodiimide compound acting as a terminal blocking agent, a carrier agent containing a phthalimide compound and benzoate compound as essential components are emulsified or dispersed in water or a solvent allows carbodiimide to be efficiently taken up into the inside of a fiber structure and to react with the carboxyl terminal group of a polymer composing the fiber structure to decrease the concentration of the terminal carboxyl group, thereby rendering hydrolysis-resistant properties.
  • a polyester-based fiber in the present invention refers to one having an ester bond in a molecular chain thereof. Aliphatic polyesters and aromatic polyesters are preferably used.
  • Examples of the aliphatic polyester include one obtained by fusing aliphatic dicarboxylic acid with aliphatic diol, a polymer selected from poly(D-lactic acid), poly(L-lactic acid), a copolymer of D-lactic acid and L-lactic acid, a copolymer of D-lactic acid and hydroxycarboxylic acid, a copolymer of L-lactic acid and hydroxycarboxylic acid and a copolymer of DL-lactic acid and a hydroxycarboxylic acid, and a blended product thereof.
  • polylactic acid containing L-lactic acid as a main component an environment conscious polyester Apexa that has been marketed by Du Pont or the like is preferably used.
  • Containing L-lactic acid as the main component here means that the aliphatic polyester contains 50 % by weight or more of L-lactic acid. Further, a terminal blocking agent may be added to the aliphatic polyester at the time of spinning and thereby some of the terminal carboxyl groups may be blocked.
  • Known methods of producing such polylactic acids include a two-step lactide method of once producing a lactide as a cyclic dimer with lactic acid as a raw material and subsequently carrying out ring-opening polymerization, and a one-step direct polymerization method of carrying out direct dehydration condensation in a solvent with lactic acid as a raw material.
  • the polylactic acid used in the present invention may be obtained by either of the methods.
  • aromatic polyester polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene naphthalate, polybutylene naphthalate or the like is used. Further, these aromatic polyesters may contain other copolymerization components and are not limited to the above polyesters.
  • copolymerization component for polyester examples include, but are not limited to, dimer diol aimed at improving alkaline resistance hydrolysis properties, a glycol component aimed at improving chromogenic properties, a multifunctional phosphorus compound aimed at rendering flame retardant properties and a sulfoisophthalic acid salt aimed at rendering cationic dye-dyeability.
  • glycol component examples include a diol compound in which an ethylene oxide is added to a compound such as 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, bisphenol A or bisphenol S, a copolymerization product of propylene oxide and ethylene oxide and polyoxyalkylene glycol.
  • phosphinates include phosphates such as (2-carboxylethyl)methylphosphinic acid, (2-methoxycarbonylethyl)methylphosphinic acid methyl ester, (2-carboxylethyl)phenylphosphinic acid, (2-methoxycarbonylethyl)phenylphosphinic acid methyl ester, (4-methoxycarbonylphenyl)phenylphosphinic acid methyl ester or ethylene glycol ester of [2-( ⁇ -hydroxy ethoxycarbonyl)ethyl]methylphosphinic acid; and phosphine oxides such as (1,2-dicarboxyethyl)dimethyl phosphine oxide, (2,3-dicarboxypropyl)dimethyl phosphine
  • sulfoisophthalic acid salt examples include an alkali metal salt of sulfoisophthalic acid, a phosphonium salt of sulfoisophthalic acid and an ester-forming derivative derived therefrom.
  • alkali metal salt of sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid or 5-lithium sulfoisophthalic acid, 5-(tetraalkyl)phosphonium sulfoisophthalic acid and an ester-forming derivative derived therefrom.
  • the polyester-based fiber used in the present invention may be, besides ordinary flat yarns, filament yarns such as false twisted yarns, strong twisted yarns, Taslan yarns, irregularly thick and fine yarns, mixed yarns or the like, and may also be a fiber of various modes such as staple fiber, tow, spun yarns, fabric or the like.
  • the polyester-based fiber used in the present invention may also form an alloy with another polymer such as a polyamide.
  • a natural fiber, regenerated fiber, semi-synthetic fiber, synthetic fiber or the like can be mixed to be used.
  • the mixing mode may be any mode of fibers-mixed spinning, threads-mixed weaving, threads-mixed knitting, or the like.
  • Examples of the mode of the fiber structure include, but are not limited to, a filament, spun yarn, fiber structure obtained formed therefrom such as a woven fabric, knitted fabric, nonwoven fabric or other manufactured article.
  • Examples of the natural fiber include a cotton fiber, kapok fiber, hemp fiber, flax fiber, cannabis fiber, ramie fiber, wool fiber, alpaca fiber, cashmere fiber, mohair fiber and silk fiber.
  • Examples of the regenerated fiber include a viscose fiber, Cupra fiber, polynosic fiber, high wet modulus rayon fiber and solvent-spun cellulose fiber.
  • Examples of the semi-synthetic fiber include an acetate fiber, diacetate fiber and triacetate fiber.
  • Examples of the synthetic fiber include a polyamide fiber, acrylic fiber, vinylon fiber, polypropylene fiber, polyurethane fiber, polyvinyl chloride fiber, polyethylene fiber and promix fiber.
  • a polyester-based fiber and other fibers can be mixed to use by any arbitrary method, but if the mixing rate of polyester-based fiber is small, effects of the present invention are small. It is therefore preferred that the mixing rate of the polyester-based fiber be 30% by weight or more. More preferred is 50% by weight or more.
  • a polyester-based fiber structure is treated with a treatment solution containing a finishing agent in which a carbodiimide-based terminal blocking agent and a carrier containing a phthalimide compound and benzoic acid compound as essential components are emulsified or dispersed in water or a solvent.
  • a finishing agent in which a carbodiimide-based terminal blocking agent and a carrier containing a phthalimide compound and benzoic acid compound as essential components are emulsified or dispersed in water or a solvent.
  • a method of treating a polyester-based fiber with a treatment solution containing a finishing agent preferably used is a method comprising placing the polyester-based fiber in a treatment solution containing a finishing agent of the present invention and then processing in a bath with the treatment solution being circulated.
  • examples of the mode of the treated product include, but are not limited to, a fabric, yarn, other manufactured article, tow and cotton batting.
  • an apparatus including, but not limited to, a wince dyeing machine, jigger dyeing machine, paddle dyeing machine, drum-type dyeing machine, liquid flow dyeing machine, air flow dyeing machine, beam dyeing machine, cheese dyeing machine and devismaier can be utilized.
  • the heat treatment time be 10 to 120 minutes.
  • the treatment be carried out at 90 to 110°C for 20 to 60 minutes.
  • the treatment be carried out at 110 to 130 °C for 20 to 60 minutes.
  • the terminal blocking agent is attached onto the fiber and taken up to disperse in the inside of the fibers.
  • the terminal blocking agent may be inadequately taken up to disperse in the inside of the fiber, and satisfactory hydrolysis-resistant properties can in some cases not be attained.
  • dehydration and drying are carried out.
  • the drying may be carried out in any condition with 100 to 140°C being preferred.
  • a heat treatment that is carried out after the drying, it is preferred to treat at 80 to 200°C. It is preferred that the treatment time be 15 seconds to 8 minutes. In the case of an aliphatic polyester, it is more preferred to treat at 90 to 140°C for 30 seconds to 5 minutes. In the case of an aromatic polyester, it is more preferred to treat at 130 to 190°C for 30 seconds to 5 minutes.
  • the treatment solution is mixed with a hydrophobic dye typified by a disperse dye, terminal blocking treatment and dyeing can be concurrently carried out.
  • a hydrophobic dye typified by a disperse dye
  • a tenter, short loop dryer, shrink surfer, steamer or cylinder dryer, or the like can be utilized, but the apparatus is not limited thereto as long as it can give heat uniformly to the fiber.
  • examples of the method of treating a polyester-based fiber with a treatment solution containing a finishing agent includes a method of giving the treatment solution containing the finishing agent to the polyester-based fiber using a device apparatus such as a mangle, followed by drying and heat treatment.
  • an ordinary mangle can be suitably used as a liquid-giving apparatus, but the apparatus is not restricted as long as it can give the solution uniformly to the fiber.
  • a foam processing machine or print method, ink jet, spray method, coating method or the like may also be used for giving the solution.
  • a tenter, short loop dryer, shrink surfer, steamer or cylinder dryer, or the like can be utilized, but the apparatus is not limited thereto as long as it can give heat uniformly to the fiber.
  • a fabric is immersed in the treatment solution containing a finishing agent and squeezed uniformly, followed by dry heat treatment.
  • the drying temperature be 80°C to 150°C.
  • the treatment time be 15 seconds to 5 minutes.
  • the terminal blocking agent may in some cases react with water in a drying step and become deactivated.
  • heat treatment after the drying be carried out at 80 to 200°C. It is preferred that the treatment time be 15 seconds to 8 minutes. In the case of an aliphatic polyester, it is more preferred to treat at 90 to 140°C for 30 seconds to 5 minutes. In the case of an aromatic polyester, it is more preferred to treat at 130 to 190°C for 30 seconds to 5 minutes. In cases where the treatment temperature is too high, polyester ends up melting. Also, in cases where the treatment time is too long, the polyester ends up being hydrolyzed during the treatment.
  • a method of wet heat treatment after giving the treatment solution containing the finishing agent of the present invention to the polyester-based fiber is preferably used.
  • the wet heat treatment as compared with the above two methods of the dry heat treatment, has better heat conduction and allows the terminal blocking agent to more efficiently react with the polyester-based fiber.
  • the wet heat treatment is carried out after giving the treatment solution using a mangle or the like.
  • a wet heat treatment apparatus an atmospheric steamer, high pressure steamer or the like can be utilized, but the apparatus is not limited thereto as long as it can give heat uniformly to the fiber.
  • a fabric is immersed in the treatment solution containing a terminal blocking agent and squeezed uniformly, followed by wet heat treatment at 80 to 130°C.
  • the treatment time be 15 seconds to 8 minutes.
  • an aromatic polyester it is more preferred to treat at 105 to 130°C for 30 seconds to 5 minutes.
  • a treatment solution containing a terminal blocking agent is mixed with a hydrophobic dye typified by a disperse dye
  • terminal blocking treatment and dyeing can be concurrently carried out.
  • the dye concentration is enhanced. Further, the number of times of undergoing a wet heat treatment step decreases and the hydrolysis of polyester is thus inhibited.
  • hydrophobic dye vat dye, indigo dye, naphthol dye or the like can also be used.
  • a carbodiimide compound used as a terminal blocking agent in the present invention may be any compound as long as it has at least one carbodiimide group.
  • a compound represented by the following general formula (I) is used.
  • R1 represents one selected from an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an allyl group and an aralkyl group with 7 to 20 carbon atoms.
  • one or more compounds may be arbitrarily selected from these carbodiimide compounds to block the carboxyl terminus of the polyester.
  • N,N'-di-2,6-diisopropylphenylcarbodiimide (TIC) and N,N'-di-cyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC) can also be suitably used.
  • TIC N,N'-di-2,6-diisopropylphenylcarbodiimide
  • DCC N,N'-di-cyclohexylcarbodiimide
  • DIC N,N'-diisopropylcarbodiimide
  • Suitable examples are “Stabaxol” I, “Stabaxol” I LF, "Stabaxol” P, and “Stabaxol” P-100, all of which are marketed under the trade name of "Stabaxol” by Rhein Chemie Japan Ltd.
  • a carrier agent used in the present invention is added for the purpose of swelling a polyester chain and efficiently taking up a terminal blocking agent into the inside of a fiber.
  • Trichlorobenzene, methylnaphthalene and the like which have been conventionally used, have strong odor and readily cause carrier spots. Thus, there is concern about the odor and quality of a final manufactured article in conjunction with worsened working environment. As a result of intensive studied conducted for solving such problems, it has been found that use of a phthalimide compound and benzoate compound enables a terminal blocking agent to be efficiently taken up into the inside of a polyester fiber.
  • the phthalimide compound used in the present invention is a compound having a phthalimide group.
  • Preferred is phthalimide having an aliphatic or aromatic alkyl group or the like in the N group of phthalimide.
  • substituent group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl and naphthal.
  • N-phthalimide having low molecular weight aliphatic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
  • N-butylphthalimide is preferably used in that it has excellent compatibility with the carbodiimide compound.
  • the benzoate is formed from benzoic acid and aliphatic or aromatic alcohol. Examples of the benzoate include ethyl benzoate, methyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate and phenyl benzoate.
  • benzyl benzoate, phenyl benzoate or the like is more preferred.
  • benzyl benzoate that has molecular weight close to TIC, which is a terminal blocking agent, and can be inexpensively obtained.
  • a mixing ratio of the phthalimide compound with the the benzoate compound is, based on 50 parts by weight of phthalimide compound, preferably 10 parts by weight to 50 parts by weight of benzoate compound, more preferably 15 parts by weight to 40 parts by weight of benzoate compound, and still more preferably 20 parts by weight to 30 parts by weight of benzoate compound.
  • two or more types of the phthalimide compounds and two or more types of the benzoate compounds may be used.
  • UNIVADINE PB As a mixture of N-phthalimide and benzoate, UNIVADINE PB has been marketed by Huntsman Corporation and can be suitably used.
  • the ratio of the carbodiimide compound with the mixed carrier agent is, based on 25 parts by weight of the carbodiimide compound, preferably 20 parts by weight to 35 parts by weight of the mixed carrier agent and more preferably 25 to 30parts by weight of the mixed carrier agent.
  • the finishing agent for a polyester-based fiber structure by the present invention is made by emulsifying or dispersing the above carbodiimide compound and a carrier agent containing a benzoic acid compound and phthalimide compound as essential components in water or a solvent. It is preferred that at least one surfactant selected from either a nonionic surfactant or anionic surfactant be used as an emulsifying agent or dispersing agent.
  • the terminal blocking agent can, for example, be mixed with the above-mentioned carrier agent and surfactant and, as necessary, an organic solvent, and heated to form a homogeneous molten product, which is allowed to cool to obtain a self emulsification-type finishing agent which is in a liquid form at normal temperature.
  • a self emulsification-type finishing agent which is in a liquid form at normal temperature.
  • the terminal blocking agent can, for example, be mixed with the above-mentioned aliphatic hydrocarbon-based compatibilizing agent and surfactant, heated to form a homogeneous molten product which is then gradually added to heated water while stirred, to emulsify and allow to cool, thereby obtaining, similarly to the above, an emulsified product of the terminal blocking agent with water being a dispersion medium.
  • an organic solvent can, as described above, be used as necessary to the extent where the rate of taking up the carbodiimide compound is not affected.
  • this organic solvent examples include aromatic hydrocarbons such as toluene, xylene or alkyl naphthalene; ketones such as acetone or methyl ethyl ketone; alcohols such as methyl alcohol or ethyl alcohol; glycols such as ethylene glycol or propylene glycol; ethers such as dioxane; alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or ethylene glycol monoisobutyl ether; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; and halogenated hydrocarbons such as methylene chloride or chloroform. These organic solvents may be used solely or two or more types thereof may be used in combination as necessary.
  • At least one type of the surfactant selected from either a nonionic surfactant or anionic surfactant be combined to use when a terminal blocking agent composed of the carbodiimide compound is emulsified in water together with the carrier agent.
  • nonionic surfactant examples include polyoxyalkylene-type nonionic surfactant such as higher alcohol alkylene oxide adduct, alkyl phenol alkylene oxide adduct, styrenated phenol alkylene oxide adduct, fatty acid alkylene oxide adduct, polyol aliphatic ester alkylene oxide adduct, higher alkylamine alkylene oxide adduct or fatty acid amide alkylene oxide adduct; and polyol-type nonionic surfactant such as alkyl glycoside or sucrose fatty acid ester.
  • These nonionic surfactants may be used solely or two or more types thereof may be used in combination as necessary.
  • examples of the above anionic surfactant include carboxylate such as fatty acid soap; sulfate ester salt such as higher alcohol sulfate ester salt, higher alkyl polyalkylene glycol ether sulfate ester salt, sulfate ester salt of styrenated phenol alkylene oxide adduct, sulfate ester salt of alkyl phenol alkylene oxide adduct, sulfated oil, sulfated fatty acid ester, sulfated fatty acid or sulfated olefin; formalin fusion product such as alkyl benzene sulfonate, alkyl naphthalenesulfonate, naphthalenesulfonate or naphthalenesulfonic acid; sulfonate such as ⁇ -olefin sulfonate, paraffin sulfonate or sulfosuccinic acid diester salt
  • nonionic surfactant and anionic surfactant may be combined as necessary.
  • the amount of the above surfactant added is, based on 25 parts by weight of the carbodiimide compound, preferably 0.1 to 3.5 parts by weight, more preferably 0.1 to 3.0 parts by weight, and still more preferably 0.1 to 2.5 parts by weight. If the surfactant is less than 0.1 parts by weight the carbodiimide compound is not adequately emulsified and dispersed, whereas if it is more than 3.5 parts by weight a rate of taking up the carbodiimide compound might decrease.
  • a propeller-type stirring machine As equipment used emulsified dispersion for obtaining the emulsified product in the present invention, a propeller-type stirring machine, piston-type high pressure emulsification machine, homo mixer, ultrasonic emulsified dispersion machine, pressurized nozzle-type emulsification machine, high-speed rotating high shear-type stirring disperser or the like can be used. Two or more types of these equipment can be used in combination.
  • the amount of terminal blocking agent used in the present invention may be just determined in accordance with the amount of the terminal carboxyl group of a polyester-based fiber to be subjected.
  • the polyester-based fibers structure obtained by the present invention have excellent hydrolysis resistance and can be preferably used as dress shirts, blouses, pants, skirts, polo shirts, T shirts, training wear, coats, sweaters, pajamas, school uniforms, work clothes, white robes, clean room wear, unlined kimonos, underwear, linings, interlinings or the like.
  • ones subjected to the terminal blocking treatment with polyethylene terephthalate can be preferably used for uniforms for medical treatment, nursing care, food products, which uniforms require autoclaving treatment at 120°C to 130°C.
  • L-polylactic acid chips with a melting point of 166°C were dried in a vacuum dryer that was set at 105°C for 12 hours.
  • the dried chips were charged into a melt spinning machine and melt-spun at a melting temperature of 210°C, at a spinning temperature of 220°C and at a spinning speed of 4500 m/min to obtain product type 100 dtex-26 filament undrawn yarns.
  • the undrawn yarns were stretched at a preheating temperature of 100°C, at a heat set temperature of 130°C and at a draw ratio of 1.2 times, to obtain 84 dtex-26 filament drawn yarns.
  • the obtained drawn yarns were used to weave taffeta that was scoured at 80°C and subjected to dry heat set at 130°C for 1 minute to obtain a polylactic acid woven fabric.
  • PET polyethylene terephthalate
  • Poly L-lactic acid (optical purity 97% L-lactic acid) (PLA) with a weight average molecular weight of 165,000, a melting point of 170°C, and an residual lactide amount of 0.085% by weight was used as a core part A and polytrimethylene terephthalate (PTT) (melting point 228°C) containing 0.3% by weight titanium oxide with an average secondary particle size of 0.4 ⁇ m was used as a sheath part. They were separately melted at a spinning temperature of 250°C, at a core-sheath composition ratio (% by weight) of 70:30 and at a spinning speed of 3000 m/min to obtain 110 decitex, 36 filament undrawn yarns with a core-sheath complex structure.
  • PTT polytrimethylene terephthalate
  • the undrawn yarns were further stretched at a drawing speed of 800m/min, at a draw ratio of 1.3 times, at a drawing temperature of 90°C, and at a heat set temperature of 130°C to obtain 84 decitex, 48 filament drawn yarns.
  • the obtained drawn yarns were used to weave taffeta that was scoured at 80°C for 20 minutes and subjected to dry heat set at 130°C for 2 minutes to obtain a PET woven fabric.
  • a known method was used to obtain 84 dtex-24 filament polybutylene terephthalate (PBT) drawn yarns.
  • the obtained filament was used to weave taffeta that was scoured at 80°C for 20 minutes and subjected to dry heat set at 170°C for 1 minute to obtain a PBT woven fabric.
  • A/C No. 45 count (131.2 dtex) spun yarns
  • the obtained spun yarns were used to weave taffeta that was subjected to desizing at 100°C for 30 minutes, bleached and scoured at 90°C for 30 minutes, and subjected to dry heat set at 190°C for 1 minute to obtain an A/C woven fabric.
  • PET Polyethylene terephthalate
  • cotton were mixed and spun at a ratio of 40/60 by a known method to obtain No. 42 count (140.6 dtex) spun yarn A.
  • PET and cotton were mixed and spun at a ratio of 65/35 to obtain No. 45 count (131.2 dtex) spun yarn B.
  • the obtained spun yarn A and spun yarn B were used as warp and one obtained by aligning 84 dtex-26 filament PET yarns that were obtained by a known method with stretching was used as weft to obtain twill.
  • the obtained twill was subjected to desizing at 100°C for 30 minutes, bleached and scoured at 90°C for 30 minutes, and subjected to dry heat set at 190°C for 1 minute to obtain a polyethylene terephthalate/cotton (PET/C) woven fabric.
  • the mixing rate of the PET/C woven fabric was 63/37.
  • a method disclosed in Japanese Patent Application Laid-Open Publication No. 2007-169856 was used to make a 24-gauge circular knitting of a weight of 150 g/m 2 using a cationic dye-dyeable polyester fiber composed of 84 dtex-26 filament sulfonated aromatic dicarboxylic acid modified polyethylene terephthalate.
  • the obtained knit was scoured at 80°C for 20 minutes and subjected to dry heat set at 170°C for 1 minute to obtain a cationic dye-dyeable polyester (CDP) knit.
  • CDP cationic dye-dyeable polyester
  • the terminal blocking finishing agent 2 was obtained in the same manner except that the N-butylphthalimide of the terminal blocking finishing agent 1 was altered to N-butylphthalimide (Nacalai Tesque, Inc.).
  • the terminal blocking finishing agent 3 was obtained in the same manner except that the N-butylphthalimide of the terminal blocking finishing agent 1 was altered to N-propylphthalimide (Nacalai Tesque, Inc.).
  • the terminal blocking finishing agent 4 was obtained in the same manner except that the N-butylphthalimide of the terminal blocking finishing agent 1 was altered to N-benzylphthalimide (Nacalai Tesque, Inc.).
  • the terminal blocking finishing agent 5 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 1 was altered to phenyl benzoate (Nacalai Tesque, Inc.).
  • the terminal blocking finishing agent 6 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 2 was altered to phenyl benzoate.
  • the terminal blocking finishing agent 7 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 3 was altered to phenyl benzoate.
  • the terminal blocking finishing agent 8 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 4 was altered to phenyl benzoate.
  • the terminal blocking finishing agent 9 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 1 was altered to butyl benzoate (Nacalai Tesque, Inc.).
  • the terminal blocking finishing agent 10 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 2 was altered to butyl benzoate.
  • the terminal blocking finishing agent 11 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 3 was altered to butyl benzoate.
  • the terminal blocking finishing agent 12 was obtained in the same manner except that the benzyl benzoate of the terminal blocking finishing agent 4 was altered to butyl benzoate.
  • the terminal blocking finishing agent 13 was obtained in the same manner except that the bis(2,6-diisopropylphenyl)carbodiimide of the terminal blocking finishing agent 1 was altered to diisopropylcarbodiimide (Tokyo Chemical Industry Co., Ltd.).
  • the terminal blocking finishing agent 14 was obtained in the same manner except that the bis(2,6-diisopropylphenyl)carbodiimide of the terminal blocking finishing agent 1 was altered to dicyclohexylcarbodiimide (Tokyo Chemical Industry Co., Ltd.).
  • the terminal blocking 15 was obtained in the same manner as the terminal blocking finishing agent 1 using 20.0 parts by weight of bis(2,6-diisopropylphenyl)carbodiimide, 15.0 parts by weight of trichlorobenzene (Nacalai Tesque, Inc.), 2.0 parts by weight of sulfated castor oil and 20.0 parts by weight of water.
  • the terminal blocking finishing agent 16 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to methylnaphthalene.
  • the terminal blocking finishing agent 17 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to benzyl benzoate.
  • the terminal blocking finishing agent 18 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to phenyl benzoate.
  • the terminal blocking finishing agent 19 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to butyl benzoate.
  • the terminal blocking finishing agent 20 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to N-butylphthalimide.
  • the terminal blocking finishing agent 21 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to N-ethylphthalimide.
  • the terminal blocking finishing agent 22 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to N-propylphthalimide.
  • the terminal blocking finishing agent 23 was obtained in the same manner except that the trichlorobenzene of the terminal blocking finishing agent 15 was altered to N-benzylphthalimide.
  • the terminal blocking finishing agent 24 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 1.0 part by weight and the amount of N-butylphthalimide added was altered to 14 parts by weight in the terminal blocking finishing agent 1.
  • the terminal blocking finishing agent 25 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 9.0 parts by weight and the amount of N-butylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 1.
  • the terminal blocking finishing agent 26 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 1.0 part by weight and the amount of N-butylphthalimide added was altered to 14 parts by weight in the terminal blocking finishing agent 5.
  • the terminal blocking finishing agent 27 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 9.0 parts by weight and the amount of N-butylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 5.
  • the terminal blocking finishing agent 28 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 1.0 part by weight and the amount of N-benzylphthalimide added was altered to 14 parts by weight in the terminal blocking finishing agent 4.
  • the terminal blocking finishing agent 29 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 9.0 parts by weight and the amount of N-benzylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 4.
  • the terminal blocking finishing agent 30 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 1.0 part by weight and the amount of N-benzylphthalimide added was altered to 14 parts by weight in the terminal blocking finishing agent 8.
  • the terminal blocking finishing agent 31 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 9.0 parts by weight and the amount of N-benzylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 8.
  • the terminal blocking finishing agent 32 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 11 parts by weight and the amount of N-butylphthalimide added was altered to 22 parts by weight in the terminal blocking finishing agent 1.
  • the terminal blocking finishing agent 33 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 3.0 parts by weight and the amount of N-butylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 1.
  • the terminal blocking finishing agent 34 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 11 parts by weight and the amount of N-butylphthalimide added was altered to 22 parts by weight in the terminal blocking finishing agent 5.
  • the terminal blocking finishing agent 35 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 3.0 parts by weight and the amount of N-butylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 5.
  • the terminal blocking finishing agent 36 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 11 parts by weight and the amount of N-benzylphthalimide added was altered to 22 parts by weight in the terminal blocking finishing agent 4.
  • the terminal blocking finishing agent 37 was obtained in the same manner except that the amount of benzyl benzoate added was altered to 3.0 parts by weight and the amount of N-benzylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 4.
  • the terminal blocking finishing agent 38 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 11 parts by weight and the amount of N-benzylphthalimide added was altered to 22 parts by weight in the terminal blocking finishing agent 8.
  • the terminal blocking finishing agent 39 was obtained in the same manner except that the amount of phenyl benzoate added was altered to 3.0 parts by weight and the amount of N-benzylphthalimide added was altered to 6.0 parts by weight in the terminal blocking finishing agent 8.
  • the present invention has a beneficial effect on polyesters other than PET.
  • Example 21 The PET fabric is immersed in the treatment solution below, squeezed out excess treatment solution using a mangle (pick up rate: 82%), dried for two minutes in a tenter that was set at 130°C, followed by heat treatment for another three minutes in a tenter that was set at 170°C.
  • the PET fabric after the heat treatment was cleaned in warm water of 60°C containing a nonionic surfactant, Gran-up US-20 (Sanyo Chemical Industries, Ltd.) 0.5 g/L for 10 minutes.
  • the PET fabric after the cleaning was dried for two minutes in a tenter that was set at 130°C.
  • Example 22 Terminal blocking agent :25 g/L Benzyl benzoate :5.2 g/L N-butylphthalimide :10.5 g/L Sulfated castor oil :2.5 g/L
  • Example 21 the PET fabric was altered to the PLA fabric; the drying temperature was altered to 110°C from 130°C and the temperature of the dry heat treatment was altered to 130°C from 170°C.
  • the hydrolysis test was carried out by the same method as described in Example 15.
  • Example 23 The same treatment as described in Example 22 was carried out except that the PLA fabric was altered to the PLA/PTT fabric.
  • Example 24 The same treatment as described in Example 21 was carried out except that the PET fabric was altered to the PBT fabric.
  • Example 25 The same treatment as described in Example 21 was carried out except that the PET fabric was altered to the PET/C fabric.
  • Example 26 The same treatment as described in Example 22 was carried out except that the PLA fabric was altered to the A/C fabric.
  • Example 27 The same treatment as described in Example 21 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • Example 28 The same treatment as described in Example 22 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • Example 29 The same treatment as described in Example 23 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • Example 30 The same treatment as described in Example 24 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • Example 31 The same treatment as described in Example 25 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • Example 32 The same treatment as described in Example 26 was carried out except that the heat treatment method was altered to steaming treatment by saturated steam of 102°C from the dry heat treatment.
  • the dry heat treatment was also found to be able to render good wet heat durability.
  • the wet heat treatment was also found to be able to render good wet heat durability (Table 5).
  • Example 37 the long fabric was confirmed to have good wet heat durability when processed using the liquid flow dyeing machine. No problem such as listing or ending was observed (Table 6).
  • Example 38 the fabric was confirmed to have good wet heat durability when processed with the terminal blocking finishing agent 40 (Table 7).
  • Example 33 Example 34
  • Example 35 Example 36
  • Example 37 Conditions Fabric treated PET PLA PLA/PTT PBT PET Treatment solution Composition of treatment solution Terminal blocking agent TIC TIC TIC TIC TIC Carrier agent Benzoate Benzyl benzoate Benzyl benzoate Benzyl benzoate Benzyl benzoate N-alkyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide N-butyl phthalimide Others Emulsifying agent Sulfated castor oil Sulfated castor oil Sulfated castor oil Sulfated castor oil Sulfated castor oil Sulfated castor oil Dye Dianix Tuxedo Black Fconc.

Claims (9)

  1. Agent de finition pour une structure fibreuse à base de polyester, ledit agent de finition comprenant un composé carbodiimide et un agent de support émulsionné ou dispersé dans de l'eau ou un solvant, ledit agent de support contenant un composé benzoate et un composé phtalimide en tant que composants essentiels.
  2. Agent de finition pour une structure fibreuse à base de polyester selon la revendication 1, dans lequel ledit composé carbodiimide est un composé représenté par la formule générale (I) :
    Figure imgb0016
     dans laquelle R1 représente l'un choisi parmi un groupe alkyle ayant 1 à 20 atomes de carbone, un groupe cycloalkyle ayant 5 à 12 atomes de carbone, un groupe aryle ayant 6 à 20 atomes de carbone, un groupe allyle et un groupe aralkyle ayant 7 à 20 atomes de carbone.
  3. Agent de finition pour une structure fibreuse à base de polyester selon la revendication 1 ou 2, dans lequel ledit carbodiimide est au moins l'un choisi parmi le N,N'-di-2,6-diisopropylphénylcarbodiimide, le N,N'-dicyclohexylcarbodiimide et le N,N'-diisopropylcarbodiimide.
  4. Agent de finition pour une structure fibreuse à base de polyester selon l'une quelconque des revendications 1 à 3, dans lequel ledit agent de support comprend du benzoate de benzyle et du N-butylphtalimide en tant que dits composants essentiels.
  5. Procédé de production d'une structure fibreuse à base de polyester, ledit procédé comprenant le traitement de la structure fibreuse à base de polyester avec une solution comprenant l'agent de finition selon l'une quelconque des revendications 1 à 4, ledit agent de finition étant ainsi capté à l'intérieur de ladite structure fibreuse à base de polyester.
  6. Procédé de production d'une structure fibreuse à base de polyester selon la revendication 5, ledit procédé comprenant, dans l'ordre mentionné, l'application d'une solution de traitement contenant ledit agent de finition à la ou aux fibres à base de polyester de façon que soit effectué ledit captage dudit agent de finition ; une étape de séchage ; et une étape de traitement à la chaleur.
  7. Procédé de production d'une structure fibreuse à base de polyester selon la revendication 5, ledit procédé comprenant l'introduction de la ou des fibres à base de polyester dans une solution de traitement contenant ledit agent de finition pour que la ou les fibres soient traitées dans un bain de façon que soit effectué ledit captage dudit agent de finition cependant que ladite solution de traitement circule.
  8. Procédé de production d'une structure fibreuse à base de polyester selon la revendication 5, ledit procédé comprenant l'application d'une solution de traitement contenant ledit agent de finition à la ou aux fibres à base de polyester de façon que soit effectué ledit captage dudit agent de finition ; et ensuite la soumission de ladite ou desdites fibres à base de polyester à un traitement à la chaleur humide.
  9. Structure fibreuse à base de polyester obtenue par ledit procédé selon l'une quelconque des revendications 5 à 8, dans laquelle la concentration dudit agent de finition diminue depuis une couche extérieure en direction d'une couche intérieure dans la section transversale d'une fibre isolée parmi ladite ou lesdites fibres à base de polyester.
EP11847941.9A 2010-12-16 2011-12-14 Agent de traitement pour structure fibre polyester et procédé de fabrication de structure fibre polyester qui utilise ledit agent Active EP2653605B1 (fr)

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WO2012081596A1 (fr) 2012-06-21
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