WO2016104573A1 - Fiber structure and production method for same - Google Patents
Fiber structure and production method for same Download PDFInfo
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- WO2016104573A1 WO2016104573A1 PCT/JP2015/085959 JP2015085959W WO2016104573A1 WO 2016104573 A1 WO2016104573 A1 WO 2016104573A1 JP 2015085959 W JP2015085959 W JP 2015085959W WO 2016104573 A1 WO2016104573 A1 WO 2016104573A1
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- WIPO (PCT)
- Prior art keywords
- fiber structure
- polyurethane
- elastic yarn
- diisocyanate
- yarn made
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Classifications
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- 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
- D06M13/165—Ethers
-
- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
Definitions
- the present invention relates to a fiber structure excellent in deodorizing properties, and also relates to a production method for obtaining a fiber structure having excellent deodorizing properties.
- Polyurethane-based elastic fibers are widely used for stretchable clothing and industrial materials such as legwear, innerwear, sportswear and swimwear because of their excellent stretch properties.
- textile products for deodorizing unpleasant odors such as sweaty odors and aging odors in response to a more comfortable living environment, and various technical improvements have been proposed. .
- Patent Literature As a method for imparting deodorant fine particles to the fiber surface, a material in which porous fine particles such as titanium oxide and zeolite having a photocatalytic function are fixed to the fiber surface with a binder such as silicone has been proposed (Patent Literature). 1).
- a binder such as silicone
- Patent Document 2 a method in which an ethylenically unsaturated organic acid is graft-polymerized on a polyester fiber has been proposed (Patent Document 2).
- Patent Document 2 a method in which an ethylenically unsaturated organic acid is graft-polymerized on a polyester fiber.
- a metal oxide and / or a composite metal oxide containing hinokitiol and at least one element selected from Zn, Si, Cu, Ni, Fe, Al, and Mg as a deodorant component to be included in the fiber
- Patent Document 3 a method of kneading into a polyurethane elastic yarn when dry spinning is performed.
- the deodorant component dropped out, and the sufficient deodorization performance could not be maintained.
- the present invention solves the above-mentioned problems of the prior art and provides a fiber structure excellent in deodorizing effect against ammonia, acetic acid and the like, which are main components of sweat odor and aging odor, and a method for producing the same. It is.
- a method for producing a fiber structure wherein a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is padded with at least one of alkyldiphenyl ether compounds.
- the present invention it is possible to provide a fiber structure having excellent deodorizing performance against ammonia, acetic acid and the like, which are main components of sweat odor and aging odor.
- the fiber structure of the present invention includes an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate, and includes at least one alkyldiphenyl ether compound.
- the fiber structure may have any structure and shape, and examples thereof include a fabric-like material, a belt-like material, a string-like material, and a thread-like material.
- a fabric-like woven or knitted fabric or a material including a nonwoven fabric is used, and a material including a composite material including such a fiber structure may be used.
- the fiber structure of the present invention contains an elastic yarn made of polyurethane, which will be described later, and may contain synthetic fiber, regenerated fiber, semi-synthetic fiber, natural fiber, etc. as fibers other than the elastic yarn made of polyurethane.
- the elastic yarn made of polyurethane contained in the fiber structure is preferably contained in an amount of 1% or more, more preferably 10% or more.
- the fiber structure is preferably contained in an amount of 90% or less, but may be a fiber structure containing only elastic yarns made of polyurethane and no other fibers.
- Synthetic fibers include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyacrylonitrile fibers, and the like.
- Polyester fibers include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and the like, and those obtained by copolymerizing a third component such as isophthalic acid.
- Examples of regenerated fibers and semi-synthetic fibers include rayon and acetate, and examples of natural fibers include cotton, hemp, wool, and silk.
- These fibers may be either short fibers or long fibers, and may be used singly or in combination of two or more as mixed fiber, mixed spinning, composite processed yarn, or the like. Further, it can be used as a composite processed yarn such as covering of these synthetic fibers or natural fibers and an elastic yarn made of polyurethane, air entanglement, intertwisting, composite false twisting or core span yarn.
- the fiber structure of the present invention contains at least one alkyldiphenyl ether compound.
- alkyl diphenyl ether compound those represented by the general formula (1) are preferably used.
- R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms.
- R 3 and R 4 are each independently M selected from H, Na, K, Mg and Ca. -SO 3 M.
- m and n are integers of 0 to 5, and either n or m is 1 or more, p is an integer of 0 to (5-m), and q is 0 to (It is an integer of (5-n).
- R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms.
- “independently” indicates that when m + n is 2 or more, the carbon numbers of the respective alkyl groups may all be different. It is preferable that the alkyl group has 20 or less carbon atoms because of good solubility in water.
- R 3 and R 4 are each independently —SO 3 M having M selected from H, Na, K, Mg and Ca.
- —SO 3 M represents a combination of SO 3 — and counter ion M.
- M is H, sulfonic acid is used, and when M is any of Na, K, Mg, and Ca, sulfonate is used.
- “independently” indicates that when p + q is 2 or more, Ms selected from H, Na, K, Mg, and Ca may be all different for each —SO 3 M.
- the alkyl group R 1 and the alkyl group R 2 may be either linear or branched, and the alkyl group R 1 and the alkyl group R 2 are conditions under which hydrogen on the benzene ring can be substituted. It can be located anywhere as long as it meets.
- sulfonic acid or a sulfonate is preferably substituted at any position of the benzene ring (that is, p + q is 1 or more in the general formula (1)).
- the presence of the sulfonic acid group can be expected to obtain a higher deodorizing effect.
- R 1 and R 2 , R 3 and R 4 can be located at any position as long as the hydrogen on the benzene ring satisfies a substitutable condition.
- the total of p and q is more preferably 3 or less from the viewpoint of production efficiency.
- the alkyl diphenyl ether compound of the present invention can be used in combination of at least one or two or more.
- the mass ratio of the alkyldiphenyl ether compound contained in the fiber structure of the present invention is preferably in the range of 0.1 to 100% by mass with respect to the mass of the elastic yarn made of polyurethane.
- the place where the alkyldiphenyl ether-based compound is contained may be adhered over the entire fiber structure, or may be locally adhered to the elastic yarn made of polyurethane. If it is less than 0.1% by mass, a sufficient deodorizing effect cannot be exhibited, and if it exceeds 100% by mass, the texture of the fiber structure is inhibited, which is not preferable. From the viewpoint of satisfying both the deodorizing effect and the texture, the content is more preferably 5.0 to 70% by mass, and further preferably 10 to 50% by mass.
- the polyurethane used for the polyurethane constituting the elastic yarn may be any polyurethane as long as it contains a structure in which the starting materials are a polymer diol and a diisocyanate, and is not particularly limited.
- the synthesis method is not particularly limited. That is, for example, it may be a polyurethane urea made from a polymer diol, diisocyanate, and a low molecular weight diamine, or a polyurethane urethane made from a polymer diol, diisocyanate, and a low molecular weight diol.
- the polymer diol compound refers to a diol compound having a number average molecular weight (hereinafter sometimes abbreviated as molecular weight) of 200 or more, and a compound having a molecular weight of less than 200 is referred to as a low molecular diol compound.
- the molecular weight of the polymer diol is preferably 1000 or more and 8000 or less, and more preferably 1500 or more and 6000 or less.
- the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule
- polyether glycol As the polymer diol, polyether glycol, polyester glycol, polycarbonate diol and the like are preferable.
- polyether glycol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.
- polyether glycol examples include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF) and Modified PTMG, a copolymer of 3-methyl-THF, modified PTMG, a copolymer of THF and 2,3-dimethyl-THF, modified PTMG, a copolymer of THF and neopentyl glycol, THF and ethylene oxide And / or a random copolymer in which propylene oxide is irregularly arranged.
- PTMG polytrimethylene ether glycol
- THF tetrahydrofuran
- Modified PTMG a copolymer of 3-methyl-THF
- modified PTMG a copolymer of THF and 2,3-dimethyl-THF
- modified PTMG a copo
- aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable for heat resistance and strength. This is preferable because an elastic yarn made of high polyurethane can be obtained.
- alicyclic diisocyanate for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexa Hydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate and the like are preferable.
- Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of elastic yarn made of polyurethane. And these diisocyanates may be used independently and may use 2 or more types together.
- a low molecular weight diamine and a low molecular weight diol as the chain extender used for polyurethane.
- Examples of the low molecular weight diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p'- Examples include methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred is ethylenediamine.
- ethylenediamine By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be easily obtained.
- a triamine compound capable of forming a crosslinked structure such as diethylenetriamine, may be added to these chain extenders to such an extent that the effect is not lost.
- the low molecular weight diol include ethylene glycol, 1,3 propanediol, 1 , 4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like are typical examples. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, the heat resistance of the diol-extended polyurethane is higher, and an elastic yarn made of polyurethane having higher strength can be obtained.
- end blockers are used in the polyurethane.
- monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, Monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.
- the fiber structure of the present invention preferably contains a metal phosphate in an elastic yarn made of polyurethane.
- a metal phosphate By including a metal phosphate, it is possible to further improve the deodorizing property against ammonia, acetic acid and the like which are main components of sweat odor and aging odor.
- the metal phosphate in the present invention is preferably an acidic phosphate of a tetravalent metal such as zirconium phosphate or titanium phosphate having a layered structure, aluminum dihydrogen phosphate, and the like from the viewpoint of deodorizing properties. More preferably, it is titanium phosphate and / or zirconium phosphate. These may be used alone or in combination of two or more.
- the content of the metal phosphate is preferably in the range of 0.5% by mass to 10% by mass with respect to the total mass of the elastic yarn made of polyurethane.
- the metal phosphate content is 0.5% by mass or more, a higher deodorizing property of ammonia gas can be obtained when the fabric is used, which is preferable. More preferably, it is 1.0 mass% or more.
- the content exceeds 10% by mass, it is not preferable in terms of deterioration of stretchability and cost. More preferably, it is 7.0 mass% or less. Considering the balance of deodorant properties, physical properties, and cost, a range of 1.5% by mass or more and 5.0% by mass or less is particularly preferable.
- the metal phosphate preferably has an average primary particle diameter of 3.0 ⁇ m or less from the viewpoint of suppressing clogging of the spinning dope into the spinneret. More preferably, it is 1.5 ⁇ m or less. Also, from the viewpoint of dispersibility, when the average primary particle size is smaller than 0.05 ⁇ m, the cohesive force increases and it becomes difficult to mix uniformly into the spinning dope, so that the average primary particle size is 0.05 ⁇ m or more. preferable. More preferably, it is 0.15 ⁇ m or more.
- the elastic yarn made of polyurethane may contain various stabilizers and pigments.
- BHT and hindered phenolic agents such as “Sumilyzer” (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., various types of “Chinubin” (registered trademark) manufactured by Ciba Geigy, etc.
- Benzotriazoles benzophenone drugs, phosphorus-based drugs such as “Sumilyzer” (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, various pigments such as iron oxide and titanium oxide, zinc oxide , Inorganic substances such as cerium oxide, magnesium oxide, calcium carbonate, carbon black, fluorine or silicone resin powders, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oil, cerium oxide, betaine and phosphoric acid It is also preferable to include various antistatic agents such as There is also preferred to have a bond with the polyurethane.
- phosphorus-based drugs such as “Sumilyzer” (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd.
- various hindered amine drugs various pigments such as iron oxide and titanium oxide, zinc oxide , Inorganic substances such as cerium oxide, magnesium oxide, calcium carbonate, carbon black, fluorine or silicone resin powders, metal soap
- nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., “Sumilyzer” manufactured by Sumitomo Chemical Co., Ltd. It is also preferable to contain a thermal oxidation stabilizer such as trade mark GA-80 and a light stabilizer such as “Sumisorb” (registered trademark) 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.
- the fiber structure of the present invention is treated in a bath with at least one of alkyldiphenyl ether compounds simultaneously with or after dyeing a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate. Can be obtained.
- a dyeing solution is prepared by mixing alkyldiphenyl ether compounds with auxiliary agents such as dyes and leveling agents used in normal dyeing, and dyeing treatment at normal dyeing temperature and time. do it.
- the temperature and time may be set separately in the bath.
- the treatment temperature in the bath is preferably in the range of 50 to 130 ° C. If it is lower than 50 ° C, the washing durability becomes insufficient, and if it exceeds 130 ° C, the texture of the fiber structure may be hindered.
- the treatment time is preferably in the range of 10 to 60 minutes.
- the pH of the solution is preferably adjusted in the range of 2.0 to 5.0.
- the pH adjustment may be any acid that is usually used in dyeing and finishing, and examples include acetic acid, formic acid, citric acid, malic acid, and the like.
- any of a liquid dyeing machine, an airflow dyeing machine, a jigger dyeing machine, a beam dyeing machine, a winch and the like may be used.
- the treatment can be performed by a pad dry cure method in which the fiber structure is squeezed and heat-treated.
- the drying temperature is preferably in the range of 100 to 150 ° C.
- the finishing set temperature is preferably in the range of 150 to 200 ° C.
- the pH of the liquid is preferably adjusted in the range of 2.0 to 5.0.
- the pH adjustment may be any acid that is usually used in dyeing and finishing, and examples include acetic acid, formic acid, citric acid, malic acid, and the like.
- a gravure roll, a knife coater, etc. may be used in addition to a general resin processing machine, and any of a drier having a mangle roll, a heat setter, etc. may be used.
- alkyldiphenyl ether compound alone or mixed with an oil agent by using an oil agent application roll or the like in an oil agent application in dry spinning or melt spinning of an elastic yarn made of polyurethane.
- Alkyl diphenyl ether compounds using an oil-applied roll when creating composite processed yarns such as synthetic fiber or natural fiber and polyurethane elastic yarn covering, air entanglement, intertwisting, false twisting, core spun yarn, etc. Can be applied alone or in combination with an oil agent.
- the initial concentration of odor components is 100 ppm ammonia, 30 ppm acetic acid, 38 ppm isovaleric acid, and 14 ppm nonenal.
- a 5L sample bag (made of film) is filled with only odor components for each component, sealed, left for 2 hours, and the residual gas concentration is measured using a gas detector tube corresponding to each component. Concentration.
- a sample (10 cm ⁇ 10 cm) used for measurement is placed in a sample bag (made of a film), filled with the odor component having the above-mentioned predetermined concentration, sealed, and the residual gas concentration after 2 hours is measured for each component. And measure this as the measured concentration.
- the measurement is performed three times, and the reduction rate of the residual gas concentration is calculated by the following formula using the average value, and expressed as the deodorization rate.
- Deodorization rate (%) of each deodorant component ((Blank test concentration ⁇ Measured concentration of each sample) / Blank test concentration)) ⁇ 100 Evaluation criteria for the deodorization rate were targeted to be 70% or more of ammonia, 70% or more of acetic acid, 85% or more of isovaleric acid, and 75% or more of nonenal.
- Example 1 Using a 28 gauge circular knitting machine, an elastic yarn made of 84 dtex 72 filament cationic dyeable polyester and polyurethane (Lycra T-127C manufactured by Toray Operontex Co., Ltd.) 44 dtex was used to form a bare knitted fabric.
- Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester.
- the obtained knitted fabric is made into a dyeing solution under the following conditions, and is subjected to treatment in a bath at 120 ° C. for 30 minutes at the same time as dyeing, then soaping, washing with hot water as usual, then drying at 130 ° C., 180 ° C. Finishing set in 1 minute.
- Dye Kayacrill Black BS-ED (Nippon Kayaku) Sodium butyldiphenyl ether disulfonate represented by the following formula (2)
- pH adjuster 90% acetic acid 1g / L
- Table 1 The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
- Example 2 The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Thereafter, the liquid was once drained and treated in a bath with a treatment solution of the following conditions at 80 ° C. for 20 minutes, then soaped, washed with hot water as usual, and then dried at 130 ° C., 180 ° C. for 1 minute. Finished the set.
- Sodium dodecyl diphenyl ether disulfonate represented by the following formula (3)
- pH adjuster 90% acetic acid 1g / L
- Table 1 The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
- Example 3 The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Then, after soaping, washing with hot water and drying at 130 ° C. as usual, using a treatment liquid adjusted under the following conditions, dipping / niping with a mangle at a drawing ratio of 70%, and drying at 130 ° C. Then, finish setting was performed at 180 ° C. for 1 minute.
- pH adjuster citric acid 2g / L
- Table 1 shows the details of the obtained knitted fabric, and Table 2 shows the results of evaluating deodorizing properties after 10 times of raw fabric before washing.
- Example 4 Using a 28 gauge circular knitting machine, 84 dtex 72 filament cationic dyeable polyester and elastic yarn 44 dtex made of polyurethane containing 3% by mass of titanium phosphate as a metal phosphate were arranged to make a bare tentacle knitted fabric. Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester. Processing after dyeing was carried out in the same manner as in Example 3 except that the obtained knitted fabric was used.
- Table 1 shows the details of the obtained knitted fabric
- Table 2 shows the results of evaluating the deodorizing properties after 10 times of the raw fabric before washing.
- Example 1 The same knitted fabric as in Example 4 was used except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and sodium didodecyl diphenyl ether disulfonate represented by the formula (4) was used. The same processing was performed except that there was no.
- Table 1 shows the details of the obtained knitted fabric
- Table 2 shows the results of evaluating the deodorizing properties after 10 times of the raw fabric before washing.
- the deodorant fiber structure of the present invention is excellent in deodorizing sweat odor and aging odor, and is used for clothing such as socks, leg wear, inner, outer and sports wear, lining, interlining, narrow width tape, etc. It can be used for materials, daily life such as disposable diapers and sanitary napkins, and industrial materials.
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Abstract
Provided is a fiber structure that includes an elastic yarn comprising a polyurethane that uses a polymer diol and a diisocyanate as starting materials, and contains at least one alkyl diphenyl ether-based compound, and thus has excellent odor eliminating properties with respect to ammonia, acetic acid and the like, which are the primary components of sweat and body odor.
Description
本発明は消臭性に優れた繊維構造物に関するものであり、また優れた消臭性を有する繊維構造物を得るための製造方法に関するものである。
The present invention relates to a fiber structure excellent in deodorizing properties, and also relates to a production method for obtaining a fiber structure having excellent deodorizing properties.
ポリウレタン系弾性繊維は、その優れた伸縮特性からレッグウエア、インナーウエア、スポーツウエア、水着などの伸縮性衣料用途や産業資材用途に幅広く使用されている。近年、より快適な住環境が求められる中で、汗臭、加齢臭など不快な臭気を消臭するための繊維製品が望まれるようになってきており、様々な技術改良が提案されている。
Polyurethane-based elastic fibers are widely used for stretchable clothing and industrial materials such as legwear, innerwear, sportswear and swimwear because of their excellent stretch properties. In recent years, there has been a demand for textile products for deodorizing unpleasant odors such as sweaty odors and aging odors in response to a more comfortable living environment, and various technical improvements have been proposed. .
例えば、消臭性微粒子を繊維表面に付与するものとして、光触媒機能を有する酸化チタンやゼオライトなどの多孔質微粒子をシリコーン等のバインダーにより繊維表面に固着させたものなどが提案されている（特許文献１）。しかしながら、高い消臭性能や洗濯耐久性を得るために多量の消臭性微粒子を使用する必要があり、更にそれらを繊維に固着させるために多量のバインダーが必要になり、繊維製品の風合いを損ねる問題があった。
For example, as a method for imparting deodorant fine particles to the fiber surface, a material in which porous fine particles such as titanium oxide and zeolite having a photocatalytic function are fixed to the fiber surface with a binder such as silicone has been proposed (Patent Literature). 1). However, it is necessary to use a large amount of deodorant fine particles in order to obtain high deodorant performance and washing durability, and a large amount of binder is required to fix them to the fiber, which impairs the texture of the textile product. There was a problem.
また、繊維を構成するポリマーを改良する方法として、ポリエステル繊維にエチレン性不飽和の有機酸をグラフト重合したものなどが提案されている（特許文献２）。しかしながら、得られた繊維が加水分解により徐々に強力低下する問題があり、繊維製品として実用化できない状況であった。
Further, as a method for improving the polymer constituting the fiber, a method in which an ethylenically unsaturated organic acid is graft-polymerized on a polyester fiber has been proposed (Patent Document 2). However, there is a problem that the obtained fiber gradually decreases in strength due to hydrolysis, and cannot be put into practical use as a fiber product.
また、消臭成分を繊維中に含有せしめるものとして、ヒノキチオールとＺｎ、Ｓｉ、Ｃｕ、Ｎｉ、Ｆｅ、Ａｌ及びＭｇから選ばれた少なくとも１種の元素を含む金属酸化物及び／または複合金属酸化物とを乾式紡糸するときにポリウレタン弾性糸に練り込む方法などが提案されている（特許文献３）。しかしながら、染色加工において消臭成分が脱落し、十分な消臭性能を維持することができない状況であった。
In addition, a metal oxide and / or a composite metal oxide containing hinokitiol and at least one element selected from Zn, Si, Cu, Ni, Fe, Al, and Mg as a deodorant component to be included in the fiber There has been proposed a method of kneading into a polyurethane elastic yarn when dry spinning is performed (Patent Document 3). However, in the dyeing process, the deodorant component dropped out, and the sufficient deodorization performance could not be maintained.
本発明は、上記した従来技術の問題点を解決し、汗臭、加齢臭の主要成分であるアンモニア、酢酸などに対して消臭効果に優れた繊維構造物およびその製造方法を提供するものである。
The present invention solves the above-mentioned problems of the prior art and provides a fiber structure excellent in deodorizing effect against ammonia, acetic acid and the like, which are main components of sweat odor and aging odor, and a method for producing the same. It is.
本発明は、上記課題を解決するために、以下のいずれかの手段を採用する。
（１）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含み、かつ、アルキルジフェニルエーテル系化合物を少なくとも１つ含む繊維構造物。
（２）繊維構造物に含まれるアルキルジフェニルエーテル系化合物の質量の比率がポリウレタンからなる弾性糸の質量に対して０．１～１００質量％の範囲である上記（１）に記載の繊維構造物。
（３）アルキルジフェニルエーテル系化合物がアルキルジフェニルエーテルスルホン酸またはアルキルジフェニルエーテルスルホン酸塩である上記（１）または（２）に記載の繊維構造物。
（４）ポリウレタンからなる弾性糸が金属リン酸塩を含んでいる上記（１）～（３）のいずれかに記載の繊維構造物。
（５）金属リン酸塩がリン酸チタン、及び／または、リン酸ジルコニウムである上記（１）～（４）のいずれかに記載の繊維構造物。
（６）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、染色と同時に、または染色した後にアルキルジフェニルエーテル系化合物の少なくとも１つを用いて浴中処理する繊維構造物の製造方法。
（７）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、アルキルジフェニルエーテル系化合物の少なくとも１つを用いてパディング処理する繊維構造物の製造方法。 The present invention employs any of the following means in order to solve the above problems.
(1) A fiber structure including an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate and including at least one alkyldiphenyl ether compound.
(2) The fiber structure according to the above (1), wherein the mass ratio of the alkyldiphenyl ether compound contained in the fiber structure is in the range of 0.1 to 100% by mass with respect to the mass of the elastic yarn made of polyurethane.
(3) The fiber structure according to (1) or (2) above, wherein the alkyl diphenyl ether compound is alkyl diphenyl ether sulfonic acid or alkyl diphenyl ether sulfonate.
(4) The fiber structure according to any one of (1) to (3) above, wherein the elastic yarn made of polyurethane contains a metal phosphate.
(5) The fiber structure according to any one of (1) to (4), wherein the metal phosphate is titanium phosphate and / or zirconium phosphate.
(6) A fiber structure in which a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is treated in a bath simultaneously with or after dyeing using at least one of alkyldiphenyl ether compounds. Manufacturing method.
(7) A method for producing a fiber structure, wherein a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is padded with at least one of alkyldiphenyl ether compounds.
（１）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含み、かつ、アルキルジフェニルエーテル系化合物を少なくとも１つ含む繊維構造物。
（２）繊維構造物に含まれるアルキルジフェニルエーテル系化合物の質量の比率がポリウレタンからなる弾性糸の質量に対して０．１～１００質量％の範囲である上記（１）に記載の繊維構造物。
（３）アルキルジフェニルエーテル系化合物がアルキルジフェニルエーテルスルホン酸またはアルキルジフェニルエーテルスルホン酸塩である上記（１）または（２）に記載の繊維構造物。
（４）ポリウレタンからなる弾性糸が金属リン酸塩を含んでいる上記（１）～（３）のいずれかに記載の繊維構造物。
（５）金属リン酸塩がリン酸チタン、及び／または、リン酸ジルコニウムである上記（１）～（４）のいずれかに記載の繊維構造物。
（６）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、染色と同時に、または染色した後にアルキルジフェニルエーテル系化合物の少なくとも１つを用いて浴中処理する繊維構造物の製造方法。
（７）ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、アルキルジフェニルエーテル系化合物の少なくとも１つを用いてパディング処理する繊維構造物の製造方法。 The present invention employs any of the following means in order to solve the above problems.
(1) A fiber structure including an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate and including at least one alkyldiphenyl ether compound.
(2) The fiber structure according to the above (1), wherein the mass ratio of the alkyldiphenyl ether compound contained in the fiber structure is in the range of 0.1 to 100% by mass with respect to the mass of the elastic yarn made of polyurethane.
(3) The fiber structure according to (1) or (2) above, wherein the alkyl diphenyl ether compound is alkyl diphenyl ether sulfonic acid or alkyl diphenyl ether sulfonate.
(4) The fiber structure according to any one of (1) to (3) above, wherein the elastic yarn made of polyurethane contains a metal phosphate.
(5) The fiber structure according to any one of (1) to (4), wherein the metal phosphate is titanium phosphate and / or zirconium phosphate.
(6) A fiber structure in which a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is treated in a bath simultaneously with or after dyeing using at least one of alkyldiphenyl ether compounds. Manufacturing method.
(7) A method for producing a fiber structure, wherein a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is padded with at least one of alkyldiphenyl ether compounds.
本発明によれば、汗臭、加齢臭の主要成分であるアンモニア、酢酸などに対して優れた消臭性能を有する繊維構造物を提供することができる。
According to the present invention, it is possible to provide a fiber structure having excellent deodorizing performance against ammonia, acetic acid and the like, which are main components of sweat odor and aging odor.
以下、本発明について詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明の繊維構造物は、ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含み、かつ、アルキルジフェニルエーテル系化合物を少なくとも１つ含むものである。
The fiber structure of the present invention includes an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate, and includes at least one alkyldiphenyl ether compound.
本発明において繊維構造物は、いかなる構造、形状のものであってもよく、例えば、布帛状物、帯状物、紐状物、糸状物などが挙げられる。好ましくは布帛状の織編物や不織布を含む物が使用され、かかる繊維構造物を含む複合材料を含む物であってもよい。
In the present invention, the fiber structure may have any structure and shape, and examples thereof include a fabric-like material, a belt-like material, a string-like material, and a thread-like material. Preferably, a fabric-like woven or knitted fabric or a material including a nonwoven fabric is used, and a material including a composite material including such a fiber structure may be used.
本発明の繊維構造物は、後述するポリウレタンからなる弾性糸を含んでおり、ポリウレタンからなる弾性糸以外の繊維として、合成繊維、再生繊維、半合成繊維、天然繊維などを含んでいてもよい。繊維構造物に含まれるポリウレタンからなる弾性糸は、１％以上含まれるのが好ましく、１０％以上がより好ましい。好ましくは９０％以下含まれているものであるが、ポリウレタンからなる弾性糸のみが含まれそれ以外の繊維が含まれていない繊維構造物であってもよい。
The fiber structure of the present invention contains an elastic yarn made of polyurethane, which will be described later, and may contain synthetic fiber, regenerated fiber, semi-synthetic fiber, natural fiber, etc. as fibers other than the elastic yarn made of polyurethane. The elastic yarn made of polyurethane contained in the fiber structure is preferably contained in an amount of 1% or more, more preferably 10% or more. The fiber structure is preferably contained in an amount of 90% or less, but may be a fiber structure containing only elastic yarns made of polyurethane and no other fibers.
合成繊維としては、ポリエステル系繊維、ポリアミド系繊維、ポリエチレン系繊維、ポリプロピレン系繊維、ポリビニルアルコール系繊維、ポリ塩化ビニル系繊維、ポリアクリルニトリル系繊維などが挙げられる。ポリエステル系繊維としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレートなどが挙げられ、これらにイソフタル酸などの第三成分が共重合されてたものが挙げられる。再生繊維や半合成繊維としては、レーヨン、アセテートなどが挙げられ、天然繊維としては綿、麻、羊毛、絹などが挙げられる。これらの繊維は短繊維、長繊維のいずれでもよく、単独あるいは２種以上を混繊、混紡や複合加工糸などとして使用することができる。またこれらの合成繊維や天然繊維とポリウレタンからなる弾性糸とのカバリング、エアー交絡、合撚、複合仮撚やコアスパンヤーンなどの複合加工糸として使用することができる。
Synthetic fibers include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyacrylonitrile fibers, and the like. Polyester fibers include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and the like, and those obtained by copolymerizing a third component such as isophthalic acid. Examples of regenerated fibers and semi-synthetic fibers include rayon and acetate, and examples of natural fibers include cotton, hemp, wool, and silk. These fibers may be either short fibers or long fibers, and may be used singly or in combination of two or more as mixed fiber, mixed spinning, composite processed yarn, or the like. Further, it can be used as a composite processed yarn such as covering of these synthetic fibers or natural fibers and an elastic yarn made of polyurethane, air entanglement, intertwisting, composite false twisting or core span yarn.
本発明の繊維構造物は、アルキルジフェニルエーテル系化合物を少なくとも１つ含むものである。アルキルジフェニルエーテル系化合物は一般式（１）で示されるものが好ましく用いられる。
The fiber structure of the present invention contains at least one alkyldiphenyl ether compound. As the alkyl diphenyl ether compound, those represented by the general formula (1) are preferably used.
（式中の、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～２０のアルキル基である。Ｒ３、Ｒ４はそれぞれ独立してＨ、Ｎａ、Ｋ、Ｍｇ及びＣａから選ばれるＭを有する－ＳＯ３Ｍである。ｍ、ｎは０～５の整数であり、ｎまたはｍのいずれかは１以上である。ｐは０～（５－ｍ）の整数であり、ｑは０～（５－ｎ）の整数である。）
一般式（１）において、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～２０のアルキル基である。ここで、「それぞれ独立して」とは、ｍ＋ｎが２以上である場合において、それぞれのアルキル基の炭素数が全て異なってもよいことを示す。アルキル基の炭素数が２０以下であると水に対する溶解性が良好であるため好ましい。 (In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms. R 3 and R 4 are each independently M selected from H, Na, K, Mg and Ca. -SO 3 M. m and n are integers of 0 to 5, and either n or m is 1 or more, p is an integer of 0 to (5-m), and q is 0 to (It is an integer of (5-n).)
In the general formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms. Here, “independently” indicates that when m + n is 2 or more, the carbon numbers of the respective alkyl groups may all be different. It is preferable that the alkyl group has 20 or less carbon atoms because of good solubility in water.
一般式（１）において、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～２０のアルキル基である。ここで、「それぞれ独立して」とは、ｍ＋ｎが２以上である場合において、それぞれのアルキル基の炭素数が全て異なってもよいことを示す。アルキル基の炭素数が２０以下であると水に対する溶解性が良好であるため好ましい。 (In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms. R 3 and R 4 are each independently M selected from H, Na, K, Mg and Ca. -SO 3 M. m and n are integers of 0 to 5, and either n or m is 1 or more, p is an integer of 0 to (5-m), and q is 0 to (It is an integer of (5-n).)
In the general formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms. Here, “independently” indicates that when m + n is 2 or more, the carbon numbers of the respective alkyl groups may all be different. It is preferable that the alkyl group has 20 or less carbon atoms because of good solubility in water.
また、一般式（１）において、Ｒ３、Ｒ４はそれぞれ独立してＨ、Ｎａ、Ｋ、Ｍｇ及びＣａから選ばれるＭを有する－ＳＯ３Ｍである。ここで、－ＳＯ３Ｍとは、ＳＯ３
－と対イオンＭの組み合わせを示し、ＭがＨである場合スルホン酸を、ＭがＮａ、Ｋ、Ｍｇ及びＣａの何れかである場合スルホン酸塩であることを示す。また、「それぞれ独立して」とは、ｐ＋ｑが２以上である場合において、それぞれの－ＳＯ３ＭについてＨ、Ｎａ、Ｋ、Ｍｇ及びＣａから選ばれるＭが全て異なってもよいことを示す。
In the general formula (1), R 3 and R 4 are each independently —SO 3 M having M selected from H, Na, K, Mg and Ca. Here, —SO 3 M represents a combination of SO 3 — and counter ion M. When M is H, sulfonic acid is used, and when M is any of Na, K, Mg, and Ca, sulfonate is used. Indicates that Further, “independently” indicates that when p + q is 2 or more, Ms selected from H, Na, K, Mg, and Ca may be all different for each —SO 3 M.
一般式（１）において、アルキル基Ｒ１、アルキル基Ｒ２は直鎖状あるいは枝分かれ状のいずれであってもよく、アルキル基Ｒ１、アルキル基Ｒ２はベンゼン環の水素が置換可能な条件を満たす限り、任意の場所に位置することができる。
In the general formula (1), the alkyl group R 1 and the alkyl group R 2 may be either linear or branched, and the alkyl group R 1 and the alkyl group R 2 are conditions under which hydrogen on the benzene ring can be substituted. It can be located anywhere as long as it meets.
アルキルジフェニルエーテル系化合物としては、ベンゼン環の任意の場所にスルホン酸またはスルホン酸塩が置換している（すなわち一般式（１）においてｐ＋ｑが１以上である）ことが好ましい。スルホン酸基が存在することによって、より高い消臭効果を得ることが期待できる。Ｒ３、Ｒ４は、Ｒ１、Ｒ２について上記したのと同様、ベンゼン環の水素が置換可能な条件を満たす限り、任意の場所に位置することができる。また、ｐ、ｑの合計は生産効率の観点から３以下であることがより好ましい。
As the alkyldiphenyl ether compound, sulfonic acid or a sulfonate is preferably substituted at any position of the benzene ring (that is, p + q is 1 or more in the general formula (1)). The presence of the sulfonic acid group can be expected to obtain a higher deodorizing effect. As described above for R 1 and R 2 , R 3 and R 4 can be located at any position as long as the hydrogen on the benzene ring satisfies a substitutable condition. The total of p and q is more preferably 3 or less from the viewpoint of production efficiency.
本発明のアルキルジフェニルエーテル系化合物は、少なくとも１種または２種以上を組み合わせて用いることができる。
The alkyl diphenyl ether compound of the present invention can be used in combination of at least one or two or more.
本発明の繊維構造物に含まれるアルキルジフェニルエーテル系化合物の質量の比率は、ポリウレタンからなる弾性糸の質量に対して０．１～１００質量％の範囲であることが好ましい。ここで、アルキルジフェニルエーテル系化合物が含まれる場所については、繊維構造物全体にわたって付着していてもよいし、ポリウレタンからなる弾性糸に局在して付着していてもよい。０．１質量％未満では十分な消臭効果を発揮することができず、１００質量％を超えると繊維構造物の風合いを阻害することになり好ましくない。消臭効果と風合いの両者を満足させる観点から、５．０～７０質量％であることがより好ましく、１０～５０質量％であることがさらに好ましい。
The mass ratio of the alkyldiphenyl ether compound contained in the fiber structure of the present invention is preferably in the range of 0.1 to 100% by mass with respect to the mass of the elastic yarn made of polyurethane. Here, the place where the alkyldiphenyl ether-based compound is contained may be adhered over the entire fiber structure, or may be locally adhered to the elastic yarn made of polyurethane. If it is less than 0.1% by mass, a sufficient deodorizing effect cannot be exhibited, and if it exceeds 100% by mass, the texture of the fiber structure is inhibited, which is not preferable. From the viewpoint of satisfying both the deodorizing effect and the texture, the content is more preferably 5.0 to 70% by mass, and further preferably 10 to 50% by mass.
本発明において、弾性糸を構成するポリウレタンに使用されるポリウレタンは、出発物質がポリマージオールおよびジイソシアネートである構造を含むポリウレタンであれば任意のものであってよく、特に限定されるものではない。また、その合成法も特に限定されるものではない。すなわち、例えば、ポリマージオールとジイソシアネートと低分子量ジアミンとを原料とするポリウレタンウレアであってもよく、また、ポリマージオールとジイソシアネートと低分子量ジオールとを原料とするポリウレタンウレタンであってもよい。
In the present invention, the polyurethane used for the polyurethane constituting the elastic yarn may be any polyurethane as long as it contains a structure in which the starting materials are a polymer diol and a diisocyanate, and is not particularly limited. Also, the synthesis method is not particularly limited. That is, for example, it may be a polyurethane urea made from a polymer diol, diisocyanate, and a low molecular weight diamine, or a polyurethane urethane made from a polymer diol, diisocyanate, and a low molecular weight diol.
なお、本発明においては、ポリマージオール化合物とはジオール化合物のうち数平均分子量（以降、分子量と略すこともある）が２００以上のものをいい、分子量２００未満のものを低分子ジオール化合物という。また、ポリマージオールの分子量としては、分子量が１０００以上８０００以下が好ましく、１５００以上６０００以下の範囲にあることがさらに好ましい。
また、鎖伸長剤として水酸基とアミノ基を分子内に有する化合物を使用したポリウレタンウレアであってもよい。本発明の効果を妨げない範囲で３官能性以上の多官能性のグリコールやイソシアネート等が使用されることも好ましい。 In the present invention, the polymer diol compound refers to a diol compound having a number average molecular weight (hereinafter sometimes abbreviated as molecular weight) of 200 or more, and a compound having a molecular weight of less than 200 is referred to as a low molecular diol compound. The molecular weight of the polymer diol is preferably 1000 or more and 8000 or less, and more preferably 1500 or more and 6000 or less.
Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. It is also preferable to use trifunctional or higher polyfunctional glycols or isocyanates as long as the effects of the present invention are not hindered.
また、鎖伸長剤として水酸基とアミノ基を分子内に有する化合物を使用したポリウレタンウレアであってもよい。本発明の効果を妨げない範囲で３官能性以上の多官能性のグリコールやイソシアネート等が使用されることも好ましい。 In the present invention, the polymer diol compound refers to a diol compound having a number average molecular weight (hereinafter sometimes abbreviated as molecular weight) of 200 or more, and a compound having a molecular weight of less than 200 is referred to as a low molecular diol compound. The molecular weight of the polymer diol is preferably 1000 or more and 8000 or less, and more preferably 1500 or more and 6000 or less.
Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. It is also preferable to use trifunctional or higher polyfunctional glycols or isocyanates as long as the effects of the present invention are not hindered.
ポリマージオールとしては、ポリエーテル系グリコール、ポリエステル系グリコール、ポリカーボネートジオール等が好ましい。そして、特に柔軟性、伸度を糸に付与する観点からポリエーテル系グリコールが使用されることが好ましい。
As the polymer diol, polyether glycol, polyester glycol, polycarbonate diol and the like are preferable. In particular, polyether glycol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.
ポリエーテル系グリコールとしては、具体的には、ポリエチレングリコール、変性ポリエチレングリコール、ポリプロピレングリコール、ポリトリメチレンエーテルグリコール、ポリテトラメチレンエーテルグリコール（以下、ＰＴＭＧと略す）、テトラヒドロフラン（以下、ＴＨＦと略す）および３－メチル－ＴＨＦの共重合体である変性ＰＴＭＧ、ＴＨＦおよび２，３－ジメチル－ＴＨＦの共重合体である変性ＰＴＭＧ、ＴＨＦ及びネオペンチルグリコールの共重合体である変性ＰＴＭＧ、ＴＨＦとエチレンオキサイド及び／又はプロピレンオキサイドが不規則に配列したランダム共重合体等が挙げられる。これらポリエーテル系グリコール類の１種を使用してもよいし、また２種以上を使用してもよい。中でもＰＴＭＧまたは変性ＰＴＭＧが好ましい。
Specific examples of the polyether glycol include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF) and Modified PTMG, a copolymer of 3-methyl-THF, modified PTMG, a copolymer of THF and 2,3-dimethyl-THF, modified PTMG, a copolymer of THF and neopentyl glycol, THF and ethylene oxide And / or a random copolymer in which propylene oxide is irregularly arranged. One of these polyether glycols may be used, or two or more thereof may be used. Of these, PTMG or modified PTMG is preferred.
次にジイソシアネートとしては、ジフェニルメタンジイソシアネート（以下、ＭＤＩと略す）、トリレンジイソシアネート、１，４－ジイソシアネートベンゼン、キシリレンジイソシアネート、２，６－ナフタレンジイソシアネートなどの芳香族ジイソシアネートが、特に耐熱性や強度の高いポリウレタンからなる弾性糸を得ることができるため好適である。さらに脂環族ジイソシアネートとして、例えば、メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネート、メチルシクロヘキサン－２，４－ジイソシアネート、メチルシクロヘキサン－２，６－ジイソシアネート、シクロヘキサン－１，４－ジイソシアネート、ヘキサヒドロキシリレンジイソシアネート、ヘキサヒドロトリレンジイソシアネート、オクタヒドロ－１，５－ナフタレンジイソシアネートなどが好ましい。脂肪族ジイソシアネートは、特にポリウレタンからなる弾性糸の黄変を抑制する際に有効に使用できる。そして、これらのジイソシアネートは単独で使用してもよいし、２種以上を併用してもよい。
Next, as diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable for heat resistance and strength. This is preferable because an elastic yarn made of high polyurethane can be obtained. Furthermore, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexa Hydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of elastic yarn made of polyurethane. And these diisocyanates may be used independently and may use 2 or more types together.
次にポリウレタンに用いられる鎖伸長剤は、低分子量ジアミンおよび低分子量ジオールのうちの少なくとも１種を使用するのが好ましい。なお、エタノールアミンのような水酸基とアミノ基を分子中に有するものであってもよい。
Next, it is preferable to use at least one of a low molecular weight diamine and a low molecular weight diol as the chain extender used for polyurethane. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.
低分子量ジアミンとしては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，３－プロパンジアミン、ヘキサメチレンジアミン、ｐ－フェニレンジアミン、ｐ－キシリレンジアミン、ｍ－キシリレンジアミン、ｐ，ｐ’－メチレンジアニリン、１，３－シクロヘキシルジアミン、ヘキサヒドロメタフェニレンジアミン、２－メチルペンタメチレンジアミン、ビス（４－アミノフェニル）ホスフィンオキサイドなどが挙げられる。これらの中から１種または２種以上が使用されることが好ましい。特に好ましくはエチレンジアミンである。エチレンジアミンを用いることにより伸度および弾性回復性、さらに耐熱性に優れた糸を容易に得ることができる。これらの鎖伸長剤に架橋構造を形成することのできるトリアミン化合物、例えば、ジエチレントリアミン等を効果が失わない程度に加えてもよい
また、低分子量ジオールとしては、エチレングリコール、１，３プロパンジオール、１，４ブタンジオール、ビスヒドロキシエトキシベンゼン、ビスヒドロキシエチレンテレフタレート、１－メチル－１，２－エタンジオールなどが代表的なものである。これらの中から１種または２種以上が使用されることが好ましい。特に好ましくはエチレングリコール、１，３プロパンジオール、１，４ブタンジオールである。これらを用いると、ジオール伸長のポリウレタンとしては耐熱性がより高くなり、また、より強度の高いポリウレタンからなる弾性糸を得ることができる。 Examples of the low molecular weight diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p'- Examples include methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred is ethylenediamine. By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be easily obtained. A triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, may be added to these chain extenders to such an extent that the effect is not lost. Examples of the low molecular weight diol include ethylene glycol, 1,3 propanediol, 1 , 4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like are typical examples. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, the heat resistance of the diol-extended polyurethane is higher, and an elastic yarn made of polyurethane having higher strength can be obtained.
また、低分子量ジオールとしては、エチレングリコール、１，３プロパンジオール、１，４ブタンジオール、ビスヒドロキシエトキシベンゼン、ビスヒドロキシエチレンテレフタレート、１－メチル－１，２－エタンジオールなどが代表的なものである。これらの中から１種または２種以上が使用されることが好ましい。特に好ましくはエチレングリコール、１，３プロパンジオール、１，４ブタンジオールである。これらを用いると、ジオール伸長のポリウレタンとしては耐熱性がより高くなり、また、より強度の高いポリウレタンからなる弾性糸を得ることができる。 Examples of the low molecular weight diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p'- Examples include methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred is ethylenediamine. By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be easily obtained. A triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, may be added to these chain extenders to such an extent that the effect is not lost. Examples of the low molecular weight diol include ethylene glycol, 1,3 propanediol, 1 , 4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like are typical examples. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, the heat resistance of the diol-extended polyurethane is higher, and an elastic yarn made of polyurethane having higher strength can be obtained.
ポリウレタンには、末端封鎖剤が１種または２種以上混合使用されることも好ましい。末端封鎖剤としては、ジメチルアミン、ジイソプロピルアミン、エチルメチルアミン、ジエチルアミン、メチルプロピルアミン、イソプロピルメチルアミン、ジイソプロピルアミン、ブチルメチルアミン、イソブチルメチルアミン、イソペンチルメチルアミン、ジブチルアミン、ジアミルアミンなどのモノアミン、エタノール、プロパノール、ブタノール、イソプロパノール、アリルアルコール、シクロペンタノールなどのモノオール、フェニルイソシアネートなどのモノイソシアネートなどが好ましい。
It is also preferable that one or more end blockers are used in the polyurethane. As end-capping agents, monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, Monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.
本発明の繊維構造物はポリウレタンからなる弾性糸に金属リン酸塩を含有させることが好ましい。金属リン酸塩を含有させることによって、汗臭、加齢臭の主要成分であるアンモニア、酢酸などに対して消臭性をさらに向上させることが可能となる。
The fiber structure of the present invention preferably contains a metal phosphate in an elastic yarn made of polyurethane. By including a metal phosphate, it is possible to further improve the deodorizing property against ammonia, acetic acid and the like which are main components of sweat odor and aging odor.
本発明における金属リン酸塩は、消臭性という観点から、層状構造を有するリン酸ジルコニウムやリン酸チタン等の４価金属の酸性リン酸塩、および、トリポリリン酸二水素アルミニウム等が好ましい。より好ましくは、リン酸チタン、及び／または、リン酸ジルコニウムである。これらは、単独で使用しても良いし、２種以上を混合しても良い。
The metal phosphate in the present invention is preferably an acidic phosphate of a tetravalent metal such as zirconium phosphate or titanium phosphate having a layered structure, aluminum dihydrogen phosphate, and the like from the viewpoint of deodorizing properties. More preferably, it is titanium phosphate and / or zirconium phosphate. These may be used alone or in combination of two or more.
金属リン酸塩の含有量は、ポリウレタンからなる弾性糸の全質量に対して０．５質量％以上１０質量％以下の範囲であることが好ましい。金属リン酸塩の含有量が０．５質量％以上とすることにより、布帛とした際にさらに高いアンモニアガスの消臭性が得られるので、好ましい。より好ましくは１．０質量％以上である。一方、含有量が１０質量％を越えると、伸縮特性の悪化やコスト面で好ましくない。より好ましくは７．０質量％以下である。消臭性と物性面、コスト面というバランスを考慮すると、１．５質量％以上５．０質量％以下の範囲が特に好ましい。
The content of the metal phosphate is preferably in the range of 0.5% by mass to 10% by mass with respect to the total mass of the elastic yarn made of polyurethane. When the metal phosphate content is 0.5% by mass or more, a higher deodorizing property of ammonia gas can be obtained when the fabric is used, which is preferable. More preferably, it is 1.0 mass% or more. On the other hand, if the content exceeds 10% by mass, it is not preferable in terms of deterioration of stretchability and cost. More preferably, it is 7.0 mass% or less. Considering the balance of deodorant properties, physical properties, and cost, a range of 1.5% by mass or more and 5.0% by mass or less is particularly preferable.
金属リン酸塩は、紡糸原液の紡糸口金への詰まりを抑えるという観点から、平均一次粒子径が３．０μｍ以下のものが好ましい。より好ましくは１．５μｍ以下である。また、分散性の観点から平均一次粒子径が０．０５μｍより小さい場合、凝集力が高まり紡糸原液中に均一に混合することが困難になるため、平均一次粒子径が０．０５μｍ以上のものが好ましい。より好ましくは０．１５μｍ以上である。
The metal phosphate preferably has an average primary particle diameter of 3.0 μm or less from the viewpoint of suppressing clogging of the spinning dope into the spinneret. More preferably, it is 1.5 μm or less. Also, from the viewpoint of dispersibility, when the average primary particle size is smaller than 0.05 μm, the cohesive force increases and it becomes difficult to mix uniformly into the spinning dope, so that the average primary particle size is 0.05 μm or more. preferable. More preferably, it is 0.15 μm or more.
さらに、ポリウレタンからなる弾性糸には、各種安定剤や顔料などが含有されていてもよい。例えば、耐光剤、酸化防止剤などにＢＨＴや住友化学工業株式会社製の“スミライザー”（登録商標）ＧＡ－８０などのヒンダードフェノール系薬剤、各種のチバガイギー社製“チヌビン”（登録商標）などのベンゾトリアゾール系、ベンゾフェノン系薬剤、住友化学工業株式会社製の“スミライザー”（登録商標）Ｐ－１６などのリン系薬剤、各種のヒンダードアミン系薬剤、酸化鉄、酸化チタンなどの各種顔料、酸化亜鉛、酸化セリウム、酸化マグネシウム、炭酸カルシウム、カーボンブラックなどの無機物、フッ素系またはシリコーン系樹脂粉体、ステアリン酸マグネシウムなどの金属石鹸、また、シリコーン、鉱物油などの滑剤、酸化セリウム、ベタインやリン酸系などの各種の帯電防止剤などが含まれることも好ましく、またこれらがポリウレタンと結合を有することも好ましい。そして、特に光や各種の酸化窒素などへの耐久性をさらに高めるには、例えば、日本ヒドラジン株式会社製のＨＮ－１５０などの酸化窒素補足剤、住友化学工業株式会社製の“スミライザー”（登録商標）ＧＡ－８０などの熱酸化安定剤、住友化学工業株式会社製の“スミソーブ”（登録商標）３００♯６２２などの光安定剤を含有することも好ましい。
Furthermore, the elastic yarn made of polyurethane may contain various stabilizers and pigments. For example, BHT and hindered phenolic agents such as “Sumilyzer” (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., various types of “Chinubin” (registered trademark) manufactured by Ciba Geigy, etc. Benzotriazoles, benzophenone drugs, phosphorus-based drugs such as “Sumilyzer” (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, various pigments such as iron oxide and titanium oxide, zinc oxide , Inorganic substances such as cerium oxide, magnesium oxide, calcium carbonate, carbon black, fluorine or silicone resin powders, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oil, cerium oxide, betaine and phosphoric acid It is also preferable to include various antistatic agents such as There is also preferred to have a bond with the polyurethane. In order to further enhance the durability to light and various types of nitric oxide, for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., “Sumilyzer” manufactured by Sumitomo Chemical Co., Ltd. It is also preferable to contain a thermal oxidation stabilizer such as trade mark GA-80 and a light stabilizer such as “Sumisorb” (registered trademark) 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.
次に本発明の繊維構造物の製造方法について詳細に説明する。
Next, the method for producing the fiber structure of the present invention will be described in detail.
本発明の繊維構造物は、ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を染色と同時に、または染色した後にアルキルジフェニルエーテル系化合物の少なくとも１つを用いて浴中処理することによって得ることができる。
The fiber structure of the present invention is treated in a bath with at least one of alkyldiphenyl ether compounds simultaneously with or after dyeing a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate. Can be obtained.
染色と同時に浴中処理する場合は、通常の染色で用いられる染料、均染剤などの助剤とともに、アルキルジフェニルエーテル系化合物を混合して染色液を作成し、通常の染色温度、時間で染色処理すればよい。
When processing in the bath at the same time as dyeing, a dyeing solution is prepared by mixing alkyldiphenyl ether compounds with auxiliary agents such as dyes and leveling agents used in normal dyeing, and dyeing treatment at normal dyeing temperature and time. do it.
また染色した後に、一旦、染色液を排出し、再度、アルキルジフェニルエーテル系化合物を含む水溶液を作成し浴中処理する場合は、別途温度や時間を設定して浴中処理すればよい。かかる場合の浴中処理の温度は、５０～１３０℃の範囲が好ましい。５０℃より低いと洗濯耐久性が不十分になり、１３０℃を越えると繊維構造物の風合いを阻害する恐れがある。処理時間は、１０～６０分の範囲が好ましい。
In addition, after dyeing, once the dyeing solution is discharged and an aqueous solution containing an alkyldiphenyl ether compound is prepared again and treated in a bath, the temperature and time may be set separately in the bath. In such a case, the treatment temperature in the bath is preferably in the range of 50 to 130 ° C. If it is lower than 50 ° C, the washing durability becomes insufficient, and if it exceeds 130 ° C, the texture of the fiber structure may be hindered. The treatment time is preferably in the range of 10 to 60 minutes.
アルキルジフェニルエーテル系化合物を含む染色液や水溶液を作成する場合、液のｐＨは２．０～５．０の範囲で調整することが好ましい。ｐＨ調整は、染色・仕上げ加工で通常使用される酸であればよく、酢酸、ギ酸、クエン酸、リンゴ酸などが挙げられるがいずれを用いてもよい。
When preparing a staining solution or an aqueous solution containing an alkyldiphenyl ether compound, the pH of the solution is preferably adjusted in the range of 2.0 to 5.0. The pH adjustment may be any acid that is usually used in dyeing and finishing, and examples include acetic acid, formic acid, citric acid, malic acid, and the like.
浴中処理で用いられる装置としては、液流染色機、気流染色機、ジッガー染色機、ビーム染色機、ウインスなどいずれを用いてもよい。
As the apparatus used in the bath treatment, any of a liquid dyeing machine, an airflow dyeing machine, a jigger dyeing machine, a beam dyeing machine, a winch and the like may be used.
別の製造方法として、ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物をアルキルジフェニルエーテル系化合物の少なくとも１つを用いてパディング処理することによって得ることができる。すなわち、アルキルジフェニルエーテル系化合物を含む処理液を、繊維構造物に含浸させた後、マングルロールで絞り、熱処理するパッド・ドライ・キュア法により処理することができる。熱処理として乾燥温度は、１００～１５０℃の範囲が好ましく、仕上げセット温度は、１５０～２００℃の範囲が好ましい。アルキルジフェニルエーテル系化合物を含む処理液を作成する場合、液のｐＨは２．０～５．０の範囲で調整することが好ましい。ｐＨ調整は、染色・仕上げ加工で通常使用される酸であればよく、酢酸、ギ酸、クエン酸、リンゴ酸などが挙げられるがいずれを用いてもよい。パディング処理で用いられる装置としては、一般的な樹脂加工機の他、グラビアロール、ナイフコーターなどでもよく、マングルロールを有する乾燥機、ヒートセッターなどいずれを用いてもよい。
As another production method, it can be obtained by padding a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate using at least one alkyldiphenyl ether compound. That is, after impregnating a fiber structure with a treatment liquid containing an alkyldiphenyl ether compound, the treatment can be performed by a pad dry cure method in which the fiber structure is squeezed and heat-treated. As the heat treatment, the drying temperature is preferably in the range of 100 to 150 ° C., and the finishing set temperature is preferably in the range of 150 to 200 ° C. When preparing a treatment liquid containing an alkyl diphenyl ether compound, the pH of the liquid is preferably adjusted in the range of 2.0 to 5.0. The pH adjustment may be any acid that is usually used in dyeing and finishing, and examples include acetic acid, formic acid, citric acid, malic acid, and the like. As an apparatus used in the padding process, a gravure roll, a knife coater, etc. may be used in addition to a general resin processing machine, and any of a drier having a mangle roll, a heat setter, etc. may be used.
また、アルキルジフェニルエーテル系化合物を含む処理液を捺染糊と混合して作成し、捺染と同時に繊維構造物に付与することも可能である。
It is also possible to prepare a treatment liquid containing an alkyldiphenyl ether compound with printing paste and apply it to the fiber structure simultaneously with printing.
糸段階での製造方法として、ポリウレタンからなる弾性糸の乾式紡糸または溶融紡糸における油剤付与において、油剤付与ロールなどを用い、アルキルジフェニルエーテル系化合物を単独または油剤と混合して付与することも可能である。また、合成繊維や天然繊維とポリウレタンからなる弾性糸とのカバリング、エアー交絡、合撚、仮撚、コアスパンヤーンなどの複合加工糸を作成するときに、油剤付与ロールなどを用いアルキルジフェニルエーテル系化合物を単独または油剤と複合して付与することも可能である。
As a production method at the yarn stage, it is also possible to apply an alkyldiphenyl ether compound alone or mixed with an oil agent by using an oil agent application roll or the like in an oil agent application in dry spinning or melt spinning of an elastic yarn made of polyurethane. . Alkyl diphenyl ether compounds using an oil-applied roll when creating composite processed yarns such as synthetic fiber or natural fiber and polyurethane elastic yarn covering, air entanglement, intertwisting, false twisting, core spun yarn, etc. Can be applied alone or in combination with an oil agent.
以下、実施例をあげて本発明をさらに具体的に説明するが、本発明は以下の実施例によって限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
＜洗濯方法＞
ＳＥＫマーク繊維製品の洗濯方法（制定者：一般社団法人繊維評価技術協議会 製品認証部、改訂日：平成２６年４月１日）に記載の標準洗濯法に準拠し、ＪＩＳ Ｌ ０２１７：１９９５．「繊維製品の取扱いに関する表示記号及びその表示方法」に記載の洗い方１０３に規定される家庭電気洗濯機を使用し、４０℃の水３０Ｌに対し４０ｍＬの割合でＪＡＦＥＴ標準配合洗剤（ポリオキシエチレンアルキルエーテル及びアルファオレフィンスルホン酸ナトリウムを配合）を添加して洗濯液とし、浴比が１：３０になるよう試料および必要に応じて負荷布を投入して、５分間洗濯、脱水、２分間すすぎ洗い、脱水、２分間すすぎ洗い、脱水の工程を１回とし、これを１０回繰り返した後、吊り干しで乾燥した。
＜消臭性の評価方法＞
ＳＥＫマーク繊維製品認証基準（制定者：一般社団法人繊維評価技術協議会 製品認証部、改訂日：平成２６年４月１日）に記載の消臭性試験に準拠し、検知管法により臭気成分の消臭性評価を行なった。臭気成分としては、アンモニア、酢酸、イソ吉草酸、ノネナールを用いた。 <How to wash>
In accordance with the standard washing method described in the washing method of SEK mark textile products (established by: Product Evaluation Department, Japan Textile Evaluation Technology Council, revised date: April 1, 2014), JIS L 0217: 1995. Using a household electric washing machine specified in Washing Method 103 described in “Display Symbols and Handling Methods for Textile Products”, a JAFET standard detergent (polyoxyethylene) at a ratio of 40 mL to 30 L of water at 40 ° C. Add alkyl ether and sodium alpha olefin sulfonate) to make the washing liquid, put the sample and load cloth as necessary to make the bath ratio 1:30, wash for 5 minutes, dehydrate, rinse for 2 minutes Washing, dehydration, rinsing for 2 minutes, and dehydration were performed once, and this process was repeated 10 times, followed by drying by hanging.
<Deodorizing evaluation method>
In accordance with the deodorant test described in the SEK Mark Textile Product Certification Standard (established by: Product Evaluation Department, Textile Evaluation Technology Council, Revised Date: April 1, 2014) The deodorant evaluation of was performed. As odor components, ammonia, acetic acid, isovaleric acid, and nonenal were used.
ＳＥＫマーク繊維製品の洗濯方法（制定者：一般社団法人繊維評価技術協議会 製品認証部、改訂日：平成２６年４月１日）に記載の標準洗濯法に準拠し、ＪＩＳ Ｌ ０２１７：１９９５．「繊維製品の取扱いに関する表示記号及びその表示方法」に記載の洗い方１０３に規定される家庭電気洗濯機を使用し、４０℃の水３０Ｌに対し４０ｍＬの割合でＪＡＦＥＴ標準配合洗剤（ポリオキシエチレンアルキルエーテル及びアルファオレフィンスルホン酸ナトリウムを配合）を添加して洗濯液とし、浴比が１：３０になるよう試料および必要に応じて負荷布を投入して、５分間洗濯、脱水、２分間すすぎ洗い、脱水、２分間すすぎ洗い、脱水の工程を１回とし、これを１０回繰り返した後、吊り干しで乾燥した。
＜消臭性の評価方法＞
ＳＥＫマーク繊維製品認証基準（制定者：一般社団法人繊維評価技術協議会 製品認証部、改訂日：平成２６年４月１日）に記載の消臭性試験に準拠し、検知管法により臭気成分の消臭性評価を行なった。臭気成分としては、アンモニア、酢酸、イソ吉草酸、ノネナールを用いた。 <How to wash>
In accordance with the standard washing method described in the washing method of SEK mark textile products (established by: Product Evaluation Department, Japan Textile Evaluation Technology Council, revised date: April 1, 2014), JIS L 0217: 1995. Using a household electric washing machine specified in Washing Method 103 described in “Display Symbols and Handling Methods for Textile Products”, a JAFET standard detergent (polyoxyethylene) at a ratio of 40 mL to 30 L of water at 40 ° C. Add alkyl ether and sodium alpha olefin sulfonate) to make the washing liquid, put the sample and load cloth as necessary to make the bath ratio 1:30, wash for 5 minutes, dehydrate, rinse for 2 minutes Washing, dehydration, rinsing for 2 minutes, and dehydration were performed once, and this process was repeated 10 times, followed by drying by hanging.
<Deodorizing evaluation method>
In accordance with the deodorant test described in the SEK Mark Textile Product Certification Standard (established by: Product Evaluation Department, Textile Evaluation Technology Council, Revised Date: April 1, 2014) The deodorant evaluation of was performed. As odor components, ammonia, acetic acid, isovaleric acid, and nonenal were used.
臭気成分の初発濃度は、アンモニア１００ｐｐｍ、酢酸３０ｐｐｍ、イソ吉草酸３８ｐｐｍ、ノネナール１４ｐｐｍとする。空試験として、５Ｌサンプルバック（フィルム製）に臭気成分のみを成分毎に充填、密封し、２時間放置後、残存ガス濃度を各成分対応のガス検知管を用いて測定し、これを空試験濃度とする。次に測定に用いる試料（１０ｃｍ×１０ｃｍ）をサンプルバック（フィルム製）に入れ、前記した所定の濃度の臭気成分を充填、密封し、２時間後の残存ガス濃度を各成分対応のガス検知管で測定し、これを測定濃度とする。測定は３回行い、その平均値を用いて、下記式により、残存ガス濃度の減少率を算出し、消臭率として表記する。
The initial concentration of odor components is 100 ppm ammonia, 30 ppm acetic acid, 38 ppm isovaleric acid, and 14 ppm nonenal. As a blank test, a 5L sample bag (made of film) is filled with only odor components for each component, sealed, left for 2 hours, and the residual gas concentration is measured using a gas detector tube corresponding to each component. Concentration. Next, a sample (10 cm × 10 cm) used for measurement is placed in a sample bag (made of a film), filled with the odor component having the above-mentioned predetermined concentration, sealed, and the residual gas concentration after 2 hours is measured for each component. And measure this as the measured concentration. The measurement is performed three times, and the reduction rate of the residual gas concentration is calculated by the following formula using the average value, and expressed as the deodorization rate.
各消臭成分の消臭率（％）＝（（空試験濃度－各試料の測定濃度）／空試験濃度））×１００
消臭率の評価基準は、アンモニア７０％以上、酢酸７０％以上、イソ吉草酸８５％以上、ノネナール７５％以上を目標とした。
＜繊維構造物中の各繊維の単位当たり質量の算出方法＞
編地作製時の（各繊維の比率）設定値と、編地の単位当たり質量の実測値から求めた。 Deodorization rate (%) of each deodorant component = ((Blank test concentration−Measured concentration of each sample) / Blank test concentration)) × 100
Evaluation criteria for the deodorization rate were targeted to be 70% or more of ammonia, 70% or more of acetic acid, 85% or more of isovaleric acid, and 75% or more of nonenal.
<Calculation method of mass per unit of each fiber in fiber structure>
It was determined from the set value (ratio of each fiber) at the time of knitted fabric preparation and the actually measured value of mass per unit of the knitted fabric.
消臭率の評価基準は、アンモニア７０％以上、酢酸７０％以上、イソ吉草酸８５％以上、ノネナール７５％以上を目標とした。
＜繊維構造物中の各繊維の単位当たり質量の算出方法＞
編地作製時の（各繊維の比率）設定値と、編地の単位当たり質量の実測値から求めた。 Deodorization rate (%) of each deodorant component = ((Blank test concentration−Measured concentration of each sample) / Blank test concentration)) × 100
Evaluation criteria for the deodorization rate were targeted to be 70% or more of ammonia, 70% or more of acetic acid, 85% or more of isovaleric acid, and 75% or more of nonenal.
<Calculation method of mass per unit of each fiber in fiber structure>
It was determined from the set value (ratio of each fiber) at the time of knitted fabric preparation and the actually measured value of mass per unit of the knitted fabric.
（実施例１）
２８ゲージの丸編機を用い、８４ｄｔｅｘ７２フィラメントのカチオン可染型ポリエステルとポリウレタンからなる弾性糸（東レ・オペロンテックス(株)製 ライクラ Ｔ－１２７Ｃ）４４ｄｔｅｘを配してベア天竺編地とした。ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量は表１の通りであった。 (Example 1)
Using a 28 gauge circular knitting machine, an elastic yarn made of 84 dtex 72 filament cationic dyeable polyester and polyurethane (Lycra T-127C manufactured by Toray Operontex Co., Ltd.) 44 dtex was used to form a bare knitted fabric. Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester.
２８ゲージの丸編機を用い、８４ｄｔｅｘ７２フィラメントのカチオン可染型ポリエステルとポリウレタンからなる弾性糸（東レ・オペロンテックス(株)製 ライクラ Ｔ－１２７Ｃ）４４ｄｔｅｘを配してベア天竺編地とした。ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量は表１の通りであった。 (Example 1)
Using a 28 gauge circular knitting machine, an elastic yarn made of 84 dtex 72 filament cationic dyeable polyester and polyurethane (Lycra T-127C manufactured by Toray Operontex Co., Ltd.) 44 dtex was used to form a bare knitted fabric. Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester.
得られた編地を下記条件で染色液を作成し染色と同時に浴中処理を１２０℃、３０分間行い、次いで、通常通り、ソーピングし、湯水洗し、その後、１３０℃で乾燥し、１８０℃、１分で仕上げセットを行った。
染料：カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）
下記式（２）に示すブチルジフェニルエーテルジスルホン酸ナトリウム The obtained knitted fabric is made into a dyeing solution under the following conditions, and is subjected to treatment in a bath at 120 ° C. for 30 minutes at the same time as dyeing, then soaping, washing with hot water as usual, then drying at 130 ° C., 180 ° C. Finishing set in 1 minute.
Dye: Kayacrill Black BS-ED (Nippon Kayaku)
Sodium butyldiphenyl ether disulfonate represented by the following formula (2)
染料：カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）
下記式（２）に示すブチルジフェニルエーテルジスルホン酸ナトリウム The obtained knitted fabric is made into a dyeing solution under the following conditions, and is subjected to treatment in a bath at 120 ° C. for 30 minutes at the same time as dyeing, then soaping, washing with hot water as usual, then drying at 130 ° C., 180 ° C. Finishing set in 1 minute.
Dye: Kayacrill Black BS-ED (Nippon Kayaku)
Sodium butyldiphenyl ether disulfonate represented by the following formula (2)
ｐＨ調整剤：９０％酢酸 １ｇ／Ｌ
得られた繊維構造物の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: 90% acetic acid 1g / L
The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
得られた繊維構造物の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: 90% acetic acid 1g / L
The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
（実施例２）
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例１と同じ編地を用い、カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）で染色した後、一旦、排液し下記条件の処理液にて浴中処理を８０℃、２０分間行い、次いで、通常通り、ソーピングし、湯水洗し、その後、１３０℃で乾燥し、１８０℃、１分で仕上げセットを行った。
下記式（３）に示すドデシルジフェニルエーテルジスルホン酸ナトリウム (Example 2)
The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Thereafter, the liquid was once drained and treated in a bath with a treatment solution of the following conditions at 80 ° C. for 20 minutes, then soaped, washed with hot water as usual, and then dried at 130 ° C., 180 ° C. for 1 minute. Finished the set.
Sodium dodecyl diphenyl ether disulfonate represented by the following formula (3)
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例１と同じ編地を用い、カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）で染色した後、一旦、排液し下記条件の処理液にて浴中処理を８０℃、２０分間行い、次いで、通常通り、ソーピングし、湯水洗し、その後、１３０℃で乾燥し、１８０℃、１分で仕上げセットを行った。
下記式（３）に示すドデシルジフェニルエーテルジスルホン酸ナトリウム (Example 2)
The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Thereafter, the liquid was once drained and treated in a bath with a treatment solution of the following conditions at 80 ° C. for 20 minutes, then soaped, washed with hot water as usual, and then dried at 130 ° C., 180 ° C. for 1 minute. Finished the set.
Sodium dodecyl diphenyl ether disulfonate represented by the following formula (3)
ｐＨ調整剤：９０％酢酸 １ｇ／Ｌ
得られた繊維構造物の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: 90% acetic acid 1g / L
The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
得られた繊維構造物の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: 90% acetic acid 1g / L
The details of the obtained fiber structure are shown in Table 1, and the results of evaluating the raw fabric before washing and the deodorizing property after 10 washings are shown in Table 2.
（実施例３）
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例１と同じ編地を用い、カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）で染色した後、通常通り、ソーピングし、湯水洗し、１３０℃で乾燥した後、下記条件にて調整した処理液を用い、浸漬後、マングルで絞り率７０％でディップ／ニップした後、１３０℃で乾燥し、１８０℃、１分で仕上げセットを行った。
下記式（４）に示すジドデシルジフェニルエーテルジスルホン酸ナトリウム ３０ｇ／Ｌの水溶液 (Example 3)
The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Then, after soaping, washing with hot water and drying at 130 ° C. as usual, using a treatment liquid adjusted under the following conditions, dipping / niping with a mangle at a drawing ratio of 70%, and drying at 130 ° C. Then, finish setting was performed at 180 ° C. for 1 minute.
An aqueous solution of sodium didodecyl diphenyl ether disulfonate 30 g / L represented by the following formula (4)
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例１と同じ編地を用い、カヤクリル ブラック ＢＳ－ＥＤ（日本化薬製）で染色した後、通常通り、ソーピングし、湯水洗し、１３０℃で乾燥した後、下記条件にて調整した処理液を用い、浸漬後、マングルで絞り率７０％でディップ／ニップした後、１３０℃で乾燥し、１８０℃、１分で仕上げセットを行った。
下記式（４）に示すジドデシルジフェニルエーテルジスルホン酸ナトリウム ３０ｇ／Ｌの水溶液 (Example 3)
The same knitted fabric as in Example 1 was used, except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and dyed with Kayacrill Black BS-ED (manufactured by Nippon Kayaku). Then, after soaping, washing with hot water and drying at 130 ° C. as usual, using a treatment liquid adjusted under the following conditions, dipping / niping with a mangle at a drawing ratio of 70%, and drying at 130 ° C. Then, finish setting was performed at 180 ° C. for 1 minute.
An aqueous solution of sodium didodecyl diphenyl ether disulfonate 30 g / L represented by the following formula (4)
ｐＨ調整剤：クエン酸 ２ｇ／Ｌ
得られた編地の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: citric acid 2g / L
Table 1 shows the details of the obtained knitted fabric, and Table 2 shows the results of evaluating deodorizing properties after 10 times of raw fabric before washing.
得られた編地の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。 pH adjuster: citric acid 2g / L
Table 1 shows the details of the obtained knitted fabric, and Table 2 shows the results of evaluating deodorizing properties after 10 times of raw fabric before washing.
（実施例４）
２８ゲージの丸編機を用い、８４ｄｔｅｘ７２フィラメントのカチオン可染型ポリエステルと金属リン酸塩としてリン酸チタンを３質量％含むポリウレタンからなる弾性糸４４ｄｔｅｘを配してベア天竺編地とした。ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量は表１の通りであった。得られた編地を用いた以外は実施例３と同様の方法で染色以降の加工を実施した。 Example 4
Using a 28 gauge circular knitting machine, 84 dtex 72 filament cationic dyeable polyester and elastic yarn 44 dtex made of polyurethane containing 3% by mass of titanium phosphate as a metal phosphate were arranged to make a bare tentacle knitted fabric. Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester. Processing after dyeing was carried out in the same manner as in Example 3 except that the obtained knitted fabric was used.
２８ゲージの丸編機を用い、８４ｄｔｅｘ７２フィラメントのカチオン可染型ポリエステルと金属リン酸塩としてリン酸チタンを３質量％含むポリウレタンからなる弾性糸４４ｄｔｅｘを配してベア天竺編地とした。ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量は表１の通りであった。得られた編地を用いた以外は実施例３と同様の方法で染色以降の加工を実施した。 Example 4
Using a 28 gauge circular knitting machine, 84 dtex 72 filament cationic dyeable polyester and elastic yarn 44 dtex made of polyurethane containing 3% by mass of titanium phosphate as a metal phosphate were arranged to make a bare tentacle knitted fabric. Table 1 shows the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester. Processing after dyeing was carried out in the same manner as in Example 3 except that the obtained knitted fabric was used.
得られた編地の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。
Table 1 shows the details of the obtained knitted fabric, and Table 2 shows the results of evaluating the deodorizing properties after 10 times of the raw fabric before washing.
（比較例１）
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例４と同じ編地を用い、式（４）に示すジドデシルジフェニルエーテルジスルホン酸ナトリウムを用いなかった以外は同様の加工を実施した。 (Comparative Example 1)
The same knitted fabric as in Example 4 was used except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and sodium didodecyl diphenyl ether disulfonate represented by the formula (4) was used. The same processing was performed except that there was no.
ポリウレタンからなる弾性糸と、カチオン可染型ポリエステルとの単位当たり質量を表１の通りとした他は実施例４と同じ編地を用い、式（４）に示すジドデシルジフェニルエーテルジスルホン酸ナトリウムを用いなかった以外は同様の加工を実施した。 (Comparative Example 1)
The same knitted fabric as in Example 4 was used except that the mass per unit of the elastic yarn made of polyurethane and the cationic dyeable polyester was as shown in Table 1, and sodium didodecyl diphenyl ether disulfonate represented by the formula (4) was used. The same processing was performed except that there was no.
得られた編地の詳細を表１に、洗濯前の原布と洗濯１０回後の消臭性を評価した結果を表２に示す。
Table 1 shows the details of the obtained knitted fabric, and Table 2 shows the results of evaluating the deodorizing properties after 10 times of the raw fabric before washing.
本発明の消臭性繊維構造物は、汗臭や加齢臭の消臭に優れ、ソックス、レッグウエア、インナー、アウターやスポーツウエア等の衣料用途、裏地、芯地、細幅テープ等の衣料資材用途、紙おむつや生理用ナプキン等の生活資材用途、および産業資材用途等に使用することができる。
The deodorant fiber structure of the present invention is excellent in deodorizing sweat odor and aging odor, and is used for clothing such as socks, leg wear, inner, outer and sports wear, lining, interlining, narrow width tape, etc. It can be used for materials, daily life such as disposable diapers and sanitary napkins, and industrial materials.
Claims (7)
- ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含み、かつ、アルキルジフェニルエーテル系化合物を少なくとも１つ含む繊維構造物。 A fiber structure comprising an elastic yarn comprising a polyurethane starting from a polymer diol and a diisocyanate, and comprising at least one alkyldiphenyl ether compound.
- 繊維構造物に含まれるアルキルジフェニルエーテル系化合物の質量の比率がポリウレタンからなる弾性糸の質量に対して０．１～１００質量％の範囲である請求項１に記載の繊維構造物。 2. The fiber structure according to claim 1, wherein the mass ratio of the alkyldiphenyl ether compound contained in the fiber structure is in the range of 0.1 to 100% by mass with respect to the mass of the elastic yarn made of polyurethane.
- アルキルジフェニルエーテル系化合物がアルキルジフェニルエーテルスルホン酸またはアルキルジフェニルエーテルスルホン酸塩である請求項１または２に記載の繊維構造物。 The fiber structure according to claim 1 or 2, wherein the alkyl diphenyl ether compound is alkyl diphenyl ether sulfonic acid or alkyl diphenyl ether sulfonate.
- ポリウレタンからなる弾性糸が金属リン酸塩を含んでいる請求項１～３のいずれかに記載の繊維構造物。 The fiber structure according to any one of claims 1 to 3, wherein the elastic yarn made of polyurethane contains a metal phosphate.
- 金属リン酸塩がリン酸チタン、及び／または、リン酸ジルコニウムである請求項１～４のいずれかに記載の繊維構造物。 The fiber structure according to any one of claims 1 to 4, wherein the metal phosphate is titanium phosphate and / or zirconium phosphate.
- ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、染色と同時に、または染色した後にアルキルジフェニルエーテル系化合物の少なくとも１つを用いて浴中処理する繊維構造物の製造方法。 A method for producing a fiber structure comprising treating a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate in a bath with at least one of alkyldiphenyl ether compounds simultaneously with or after dyeing .
- ポリマージオールおよびジイソシアネートを出発物質とするポリウレタンからなる弾性糸を含む繊維構造物を、アルキルジフェニルエーテル系化合物の少なくとも１つを用いてパディング処理する繊維構造物の製造方法。 A method for producing a fiber structure, wherein a fiber structure containing an elastic yarn made of polyurethane starting from a polymer diol and a diisocyanate is padded with at least one of alkyldiphenyl ether compounds.
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| JP2016566425A JP6687923B2 (en) | 2014-12-26 | 2015-12-24 | Fiber structure and manufacturing method thereof |
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| JP2014-264186 | 2014-12-26 | ||
| JP2014264186 | 2014-12-26 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849921A (en) * | 1971-10-23 | 1973-07-14 | ||
| JPH11200148A (en) * | 1997-12-28 | 1999-07-27 | Asahi Chem Ind Co Ltd | Polyurethane elastic fiber and elastic fabric using the same |
| JP2000096434A (en) * | 1998-09-14 | 2000-04-04 | Nicca Chemical Co Ltd | Method for improving color fastness of polyamide fiber material |
| JP2006028453A (en) * | 2004-07-21 | 2006-02-02 | Nisshinbo Ind Inc | Polyurethane elastomer and elastic fiber |
| WO2013096689A1 (en) * | 2011-12-21 | 2013-06-27 | 3M Innovative Properties Company | Anti allergen composition and spray formulation comprising the same |
| JP2014000292A (en) * | 2012-06-20 | 2014-01-09 | Suminoe Textile Co Ltd | Deodorant composition and deodorant fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130101783A1 (en) * | 2011-10-19 | 2013-04-25 | E I Du Pont De Nemours And Company | Nonfluorinated soil resist, repellency, and stain resist compositions |
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2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849921A (en) * | 1971-10-23 | 1973-07-14 | ||
| JPH11200148A (en) * | 1997-12-28 | 1999-07-27 | Asahi Chem Ind Co Ltd | Polyurethane elastic fiber and elastic fabric using the same |
| JP2000096434A (en) * | 1998-09-14 | 2000-04-04 | Nicca Chemical Co Ltd | Method for improving color fastness of polyamide fiber material |
| JP2006028453A (en) * | 2004-07-21 | 2006-02-02 | Nisshinbo Ind Inc | Polyurethane elastomer and elastic fiber |
| WO2013096689A1 (en) * | 2011-12-21 | 2013-06-27 | 3M Innovative Properties Company | Anti allergen composition and spray formulation comprising the same |
| JP2014000292A (en) * | 2012-06-20 | 2014-01-09 | Suminoe Textile Co Ltd | Deodorant composition and deodorant fabric |
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| TW201627555A (en) | 2016-08-01 |
| JPWO2016104573A1 (en) | 2017-10-05 |
| JP6687923B2 (en) | 2020-04-28 |
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