WO2020250994A1 - ポリウレタン弾性繊維及びそれを含む製品、並びにポリウレタン弾性繊維用表面処理剤 - Google Patents
ポリウレタン弾性繊維及びそれを含む製品、並びにポリウレタン弾性繊維用表面処理剤 Download PDFInfo
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- D—TEXTILES; PAPER
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
- A61F13/47—Sanitary towels, incontinence pads or napkins
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
- A61F13/49—Absorbent articles specially adapted to be worn around the waist, e.g. diapers
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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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
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- 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
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- 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
- D06M2101/38—Polyurethanes
Definitions
- the present invention relates to polyurethane elastic fibers, products containing them, and surface treatment agents for polyurethane elastic fibers.
- Polyurethane elastic fibers have high elongation and excellent elastic properties.
- the polyurethane polymer is a flexible and sticky material, in the manufacturing process of a product using the polyurethane elastic fiber, when the yarn is unwound from the winding body of the polyurethane elastic fiber or when the yarn is running. Problems such as thread breakage due to frictional resistance between guides and rollers and production variations are likely to occur, and these problems are particularly remarkable when the wound yarn is used after long-term storage.
- a method of applying a treatment agent consisting of silicone oil to the yarn is known, and since silicone oil is expensive, the treatment agent is generally obtained by diluting the silicone oil with an inexpensive mineral oil. Is prepared and applied to the thread.
- Patent Document 1 a method of adding a specific amine or organic acid to a surface treatment agent for polyurethane elastic fibers obtained by diluting silicone oil with mineral oil is reported, but a basic or acidic compound is reported in the mineral oil.
- the method of adding the above has concerns about the storage stability of the treatment agent, and also has the problems of increasing the number of preparation steps and increasing the cost.
- a hydrocarbon oil (mineral oil) having a specific viscosity range is used in a specific amount or more as a means for improving the solubilization property with a surface treatment agent for polyurethane elastic fibers obtained by diluting silicone oil with mineral oil.
- a method of applying a treatment agent to a thread has been reported.
- the viscosity of the treatment agent itself becomes high, making it difficult to apply it to a stable yarn, and there are problems of mixing failure and storage stability due to the high viscosity of the treatment agent itself. is there.
- Patent Document 3 reports a method of obtaining a polyurethane elastic fiber having good leaching property by dry spinning a spinning stock solution in which a modifier composed of silicone oil and a higher fatty acid metal salt is kneaded.
- a modifier composed of silicone oil and a higher fatty acid metal salt
- the kneading of the modifier weakens the bondability between the single yarns of the multifilament, and the single yarn is peeled off from the multifilament (hereinafter, single yarn disintegration). ) Is likely to occur, and there is a problem that the single yarn loosening causes yarn breakage when using polyurethane elastic fibers such as knitting.
- JP-A-2007-270414 Japanese Unexamined Patent Publication No. 2017-110319 JP-A-2009-287126
- the problem to be solved by the present invention is a polyurethane elastic fiber having good detonability and less variation in single yarn of multifilament even if the content of silicone oil is small. It is an object of the present invention to provide a product containing the same, and a surface treatment agent for polyurethane elastic fibers suitable for producing the polyurethane elastic fibers.
- n is an integer of 2-5.
- the polyurethane elastic fiber according to the above [1], which contains the hydrocarbon compound represented by the formula (1) having n 3 in the formula [2] at 10 ppm or more and 8000 ppm or less with respect to the weight of the polyurethane elastic fiber.
- n is an integer of 2 to 5 in the formula [3].
- n is an integer of 2-5.
- the polyurethane elastic fiber according to the above [11], which contains the hydrocarbon compound represented by the formula (1) having n 3 in the formula [12] in an amount of 0.10% by weight or more and 20% by weight or less.
- Surface treatment agent e
- n is an integer of 2 to 5 in the formula [13].
- the polyurethane elastic fiber containing a specific amount of a specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good detonability even if the content of silicone oil is small and having a small amount of multifilament single yarn variation. is there. Therefore, the polyurethane elastic fiber according to the present invention can be suitably used for fabrics, sanitary material products and the like.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
- n is an integer of 2-5.
- ⁇ I a hydrocarbon compound (hereinafter, also referred to as a specific compound), which is a polyurethane elastic fiber characterized by containing 10 ppm or more and 10000 ppm or less with respect to the weight of the polyurethane elastic fiber.
- n is an integer of 2-5.
- the reason why the solubilization property is improved by setting the content of the specific compound within the specific range is not clear, but by doing so, the compound is the surface of the polyurethane elastic fiber. It is considered that the compound can be easily localized on the surface, and the elasticity can be improved due to the high fluidity of the compound on the surface.
- the content of the specific compound is less than 10 ppm, it is difficult to exert a sufficient effect of improving the unresolvability, and it is preferably 30 ppm or more from the viewpoint of obtaining higher unresolvability.
- the content exceeds 10000 ppm single yarn disintegration tends to occur, and the unraveling property with time tends to deteriorate.
- the upper limit of the content of the specific compound is preferably 9000 ppm or less, more preferably 5000 ppm or less.
- the specific compound may be contained inside the polyurethane elastic fiber or may be attached to the surface.
- the specific compound or a mixture of the specific compound and other hydrocarbon compounds may be kneaded directly into the spinning stock solution, or the specific compound or Any method may be used in which a mixture composed of the specific compound and other hydrocarbon compounds is added to the surface treatment agent and applied to the thread surface.
- the content of the specific compound in the surface treatment agent is preferably 0.10% by weight or more and 25% by weight or less, and the content of the hydrocarbon mixture is from the viewpoint of suppressing single yarn disintegration. It is preferably 20% by weight or less, and more preferably 17% by weight or less.
- n 2 to 3 in the formula
- the polyurethane elastic fiber of the present embodiment is a fiber obtained by spinning a polyurethane polymer.
- a known polyurethane reaction technique can be used.
- a high molecular weight polyol, for example, polyalkylene ether glycol and diisocyanate are reacted under the condition of excess diisocyanate to synthesize a urethane prepolymer having an isocyanate group at the terminal, and then this urethane prepolymer is subjected to a bifunctional amine or the like.
- a polyurethane polymer can be obtained by carrying out a chain extension reaction with an active hydrogen-containing compound.
- a monofunctional active hydrogen atom may be mixed with the bifunctional amine and used as a terminal terminator.
- the molar ratio of diisocyanate to polymer polyol is preferably 1.70 or less, more preferably 1.65 or less, still more preferably 1.60 or less. is there.
- various diols composed of substantially linear homo or copolymers, for example, polyester diol, polyether diol, polyester amide diol, polyacrylic diol, polythioester diol, polythioether diol, polycarbonate diol, etc.
- examples thereof include a mixture thereof and a copolymer thereof, and preferably a polyalkylene ether glycol, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, tetra.
- a copolymerized polyether glycol composed of a methylene group and a 2,2-dimethylpropylene group a copolymerized polyether glycol composed of a tetramethylene group and a 3-methyltetramethylene group, and a mixture thereof.
- polytetramethylene ether glycol and a copolymerized polyether glycol composed of a tetramethylene group and a 2,2-dimethylpropylene group are more preferable as the polymer polyol from the viewpoint of exhibiting excellent elastic function. ..
- the number average molecular weight calculated from the hydroxyl value of the polymer polyol is preferably 500 or more, more preferably 1000 or more, and even more preferably 1500 or more in order to obtain excellent elastic performance. Further, from the viewpoint of obtaining a yarn having high heat resistance, it is preferably 5000 or less, and in order to obtain more excellent heat resistance, it is preferably 3000 or less, more preferably 2500 or less.
- diisocyanate examples include aliphatic, alicyclic, and aromatic diisocyanates.
- Examples of the active hydrogen-containing compound, that is, the chain extender having a polyfunctional active hydrogen atom include hydrazine, polyhydrazine, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,3-butane.
- Diamine, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, Low molecular weight diols such as phenyldiethanolamine, ethylenediamine, 1,2-propylene diamine, 1,3-propylene diamine, 2-methyl-1,5-pentanediamine, triethylenediamine, m-xylylene diamine, piperazine, o-, m- or p-phenylenediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,6-hexamethylenediamine, N, N'-(methylenedi-4,1-phenylene) bis [2- (ethyl) Bifunctional amines such as amino) -urea] can
- Bifunctional amines are preferred over low molecular weight diols, with at least one selected from the group ethylenediamine, 1,2-propylenediamine, 1,3-diaminocyclohexane, and 2-methyl-1,5-pentadiamine 5-40.
- a mixture of ethylenediamine containing mol% is mentioned as preferable, and ethylenediamine alone is more preferable.
- Examples of the terminal terminator having a monofunctional active hydrogen atom include methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1-.
- Monoalcohols such as butanol, monoalkylamines such as isopropylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, di Examples thereof include dialkylamines such as -2-ethylhexylamine and diisopropylamine. These can be used alone or in combination. Monoalkylamines or dialkylamines, which are monofunctional amines, are preferable to monoalcohols.
- amide-based polar solvents such as dimethylformamide, dimethylsulfoxide, and dimethylacetamide can be used during the synthesis of urethane prepolymers and the reaction between urethane prepolymers and active hydrogen-containing compounds, and are preferable. It is dimethylacetamide.
- the polyurethane polymer composition may contain various stabilizers, pigments and the like.
- various stabilizers, pigments and the like For example, hindered phenol-based, benzotriazole-based, benzophenone-based, phosphorus-based, various hindered amine-based antioxidants, metal soaps such as magnesium stearate, titanium oxide, iron oxide, zinc oxide, cerium oxide, and oxidation.
- metal soaps such as magnesium stearate, titanium oxide, iron oxide, zinc oxide, cerium oxide, and oxidation.
- Inorganic substances such as magnesium, carbon black, various pigments, silver, zinc, antibacterial agents containing these compounds, deodorants, antistatic agents, nitric oxide trapping agents, thermal oxidation stabilizers, light stabilizers, etc. It may be contained.
- ester compound or a phosphoric acid ester compound composed of a condensate of alcohol and carboxylic acid or phosphoric acid may be contained in order to suppress the disintegration of the single yarn.
- ester compounds and phosphate ester compounds are trimethyl citrate, bis (2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimetate. , Dibutyl phthalate, tricresyl phosphate, diphenyl 2-ethylhexyl phosphate and the like, and any two or more of the above compounds may be used in combination.
- the polyurethane polymer thus obtained can be formed into fibers by a known dry spinning method, melt spinning method, wet spinning method, or the like to obtain polyurethane elastic fibers. Further, polyurethane polymers polymerized using different raw materials may be mixed and spun at the pre-spinning stage.
- a polyurethane spinning stock solution obtained by dissolving a polyurethane polymer in an amide-based polar solvent is used for dry spinning. Compared with melt spinning and wet spinning, dry spinning can form the strongest physical cross-linking due to hydrogen bonds between hard segments.
- the polyurethane elastic fiber of the present embodiment can be used by containing a surface treatment agent in order to reduce resistance during unwinding and friction during use.
- the surface treatment agent may be kneaded into the spinning stock solution in advance, or may be applied by a known method such as roll oiling or guide oiling before winding on a paper tube at the time of spinning. Alternatively, the surface treatment agent may be applied in the step of winding without applying the surface treatment agent and then rewinding to make another winding body.
- the content of the surface treatment agent with respect to the weight of the polyurethane elastic fiber is preferably 1.0% by weight or more and 4.0% by weight or less from the viewpoint of cost and quality, and the surface treatment agent. It is preferable that the desired effect is exhibited in the entire range of the content.
- the composition of the surface treatment agent is not particularly limited, but is limited to silicone oils such as polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, and amino-modified silicone, hydrocarbon compounds described later, mineral fine particles, for example, silica, and colloidal.
- silicone oils such as polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, and amino-modified silicone, hydrocarbon compounds described later, mineral fine particles, for example, silica, and colloidal.
- Known surface treatment agents such as higher fatty acid metal salt powders such as alumina and talc, for example, higher aliphatic carboxylic acids such as magnesium stearate and calcium stearate, higher aliphatic alcohols, paraffin, and polyethylene solid wax at room temperature. Can be used in combination.
- Polydimethylsiloxane is preferable as the silicone oil, and the kinematic viscosity at 25 ° C.
- the content of the silicone oil is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, still more preferably 1.% by weight, based on the polyurethane elastic fiber, from the viewpoint of suppressing the loosening of single yarn. It is 0% by weight or less.
- the hydrocarbon compound contained in the polyurethane elastic fiber of the present embodiment is a compound consisting only of carbon and hydrogen.
- the polyurethane elastic fiber of the present embodiment may contain a hydrocarbon compound other than the specific compound.
- the polyurethane elastic fiber of the present embodiment is represented by the sum of the peak area of the specific compound measured by GC / MS of the solution extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound.
- the area of the component having a retention time longer than that of triacontane measured under the same conditions is preferably less than 5%.
- n 2 to 5 in the formula (1).
- the polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound.
- the area of the component having a retention time longer than that of octocosan measured under the same conditions is less than 5% of the total area of the peak derived from the compound.
- a more preferable area of the component having a retention time longer than that of octocosan is less than 3%.
- the polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound.
- the area of the component having a retention time shorter than that of hexadecane measured under the same conditions is preferably less than 5%.
- the fluidity of the hydrocarbon compound is appropriate, so that the polyurethane elastic fiber is simply used. It is considered that thread loosening is less likely to occur and thread breakage is less likely to occur.
- a more preferable area of the component having a retention time shorter than that of hexadecane is less than 3%.
- the polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound.
- the area of the component having a retention time shorter than that of octadecane measured under the same conditions is preferably less than 20%. If the area of the component whose retention time is shorter than the retention time of octadecane is less than 20% of the total area of the peak derived from the hydrocarbon compound, the fluidity of the hydrocarbon becomes more appropriate, so that the polyurethane elastic fiber is simply used. It is considered that thread loosening is less likely to occur and thread breakage is less likely to occur. A more preferable area of the component having a retention time shorter than that of octadecane is less than 15%.
- the polyurethane elastic fiber of the present embodiment is a hydrocarbon represented by the sum of the peak area of the specific compound measured by GC / MS extracted with hexane by the method described later and the peak area of a hydrocarbon compound other than the specific compound.
- the area of the component contained between the retention times of octadecane and octocosan measured under the same conditions is preferably 80% or more.
- the fluidity of the hydrocarbon compound becomes more appropriate.
- the effect of improving the solvability can be further improved without increasing the occurrence rate of single yarn disintegration.
- the area of the component during the retention time of octadecane and octocosan is preferably 90% or more, more preferably 95% or more.
- the area of each component measured by the GC / MS is the same for the surface treatment agent according to another embodiment of the present invention.
- the hydrocarbon compound other than the specific compound is not particularly limited as long as it is a compound consisting only of carbon and hydrogen, but is light isoparaffin, synthetic squalane, vegetable squalane, squalane, selecin, paraffin, petrolatum, machine oil, and spindle oil. , Naften oil, liquid paraffin, liquid isoparaffin, polyalphaolefin, polyisobutylene, polybutene and the like, and one or more of them may be used. Further, the specific compound may be contained in advance among those hydrocarbon compounds.
- the total content of the specific compound and the hydrocarbon compound other than the specific compound is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, based on the yarn, from the viewpoint of suppressing loosening of single yarn. preferable.
- the polyurethane elastic fiber of the present embodiment includes natural fibers such as cotton, silk and wool, polyamide fibers such as nylon 6 and nylon 66, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate and polytetramethylene terephthalate, and cationic dyeable polyester. Interwoven with fibers, copper-ammonia recycled rayon, viscous rayon, acetate rayon, etc., or processed yarns by coating, entanglement, twisting, etc. using these fibers, and then interwoven and woven to cause spots. It is possible to obtain a high-quality fabric that does not have any quality.
- fabrics using polyurethane elastic fibers have a large production amount and are supplied as bare yarns, and are therefore suitable for warp knits that are greatly affected by the quality of the raw yarns.
- the warp knitted fabric includes a power net, a satin net, a Russell lace, a two-weight ricott, and the like.
- the fabric using the polyurethane elastic fiber of the present embodiment is used for applications such as swimwear, girdles, bras, tights, pantyhose, waistbands, body suits, spats, stretch sportswear, stretch outerwear, medical wear, stretch lining, etc. be able to.
- the polyurethane elastic fiber of the present embodiment can be suitably used for sanitary material products such as sanitary napkins and disposable diapers, has good smoothness, and has small fluctuation in friction, so that high productivity and product stability Can be obtained.
- another embodiment of the present invention is characterized by containing 0.10% by weight or more and 25% by weight or less of the specific compound of the formula (1) in which n is an integer of 2 to 5 in the formula. It is a surface treatment agent for polyurethane elastic fibers.
- the content of the specific compound of the above formula (1), in which n is an integer of 2 to 5 in the above formula is set in the above-mentioned specific range, the unfoldability of the polyurethane elastic fiber is improved. Therefore, it is considered that the specific compound can be easily localized on the surface of the polyurethane elastic fiber, and the unfoldability can be improved due to the high content of the specific compound on the surface.
- the content of the specific compound is preferably 0.10% by weight or more and 20% by weight or less, and more preferably 0.10% by weight or more and 17% by weight or less.
- the hydrocarbon compound contained in the surface treatment agent for fibers of the present embodiment is a compound consisting of only carbon and hydrogen.
- the surface treatment agent for fibers of the present embodiment may contain a hydrocarbon compound other than the specific compound.
- Hydrocarbon compounds other than the specific compounds include light isoparaffin, synthetic squalane, vegetable squalane, squalane, ceresin, paraffin, petrolatum, machine oil, spindle oil, naphthenic oil, liquid paraffin, liquid isoparaffin, polyalphaolefin, and polyisobutylene. , Polybutene and the like, and one kind or two or more kinds may be used. Further, the specific compound may be contained in advance in those hydrocarbon compounds.
- the surface treatment agent for fibers of the present embodiment preferably further contains silicone oil in an amount of 20% by weight or more and 70% by weight or less.
- the kinematic viscosity at 25 ° C. is preferably 15 mm 2 / s or less from the viewpoint that polydimethylsiloxane can be raised and friction can be reduced.
- the surface treatment agent for fibers of the present embodiment includes polyester-modified silicone, polyether-modified silicone, amino-modified silicone, mineral fine particles, for example, silica.
- Higher fatty acid metal salt powders such as colloidal alumina and talc, for example, higher aliphatic carboxylic acids such as magnesium stearate and calcium stearate, higher aliphatic alcohols typified by isostearyl alcohol, paraffin, and solids at room temperature such as polyethylene.
- a known surface treatment agent such as wax can be used in combination.
- ester compound or a phosphoric acid ester compound composed of a condensate of alcohol and a carboxylic acid or a phosphoric acid may be contained in the surface treatment agent for fibers in order to suppress the loosening of the single yarn.
- ester compounds and phosphate ester compounds are trimethyl citrate, bis (2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimetate. , Dibutyl phthalate, tricresyl phosphate, diphenyl 2-ethylhexyl phosphate and the like, and any two or more of the above compounds may be used in combination.
- the surface treatment agent for fibers of the present embodiment can be applied by known methods such as roll oiling, guide oiling, and spray oiling.
- the area of the component is the area of the component C18 or less
- the area of the component having the retention time between the retention time of hexadecane and triacontane is the area of the component of C16-C30
- octadecane is the area of the component having a retention time during the retention time of triacontane.
- the area of the component having a retention time during the retention time of triacontane is the area of the component of C18-C30
- the area of the component having the retention time between the retention times of octadecane and octocosan is the area of the component of C18-C28. Calculated as a percentage.
- each area components not derived from the hydrocarbon compound were removed by GC / MS.
- the peak of the hydrocarbon compound may be detected broadly. In that case, the start point is the start of the peak rise, and the end point is the point where the detected value of the peak begins to disappear to a negligible level.
- the area was calculated from the baseline connecting the end points with a straight line.
- the polyurethane elastic fiber After winding the polyurethane elastic fiber around a paper tube so that the winding width is 60 mm and the total weight is 3 kg, the polyurethane elastic fiber is allowed to stand in an environment of 20 ° C. and 60% RH for 2 days, and then 2 cm from the paper tube.
- the thread is peeled off to make a measurement sample, the thread is passively unwound at 15 m / min in the direction of the end face of the measurement sample, the tension at that time is measured for 5 minutes, the average value is taken as the unwinding tension, and 7 according to the following evaluation criteria. Judgment was made in stages.
- Negative unraveling refers to a method of unraveling in a vertical manner. 7:10 g or less 6: 10 g or more and less than 13 g 5: 13 g or more and less than 15 g 4: 15 g or more and less than 25 g 3: 25 g or more and less than 30 g 2:: 30 g or more and less than 35 g 1: 35 g or more or thread breakage
- the measurement was performed 5 times with a set of 10 threads per same sample, the number of loose threads out of a total of 50 threads was counted, the occurrence rate was calculated, and the evaluation was made in the following 7 stages. It can be expected that the lower the occurrence rate of single yarn loosening, the less likely it is that yarn breakage due to single yarn cracking will occur when the polyurethane elastic fiber is used.
- Example 1 2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained. After cooling this to room temperature, dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution.
- a polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa ⁇ s (30 ° C.) was obtained.
- This undiluted spinning solution is dry-spun at a winding speed of 500 m / min and a hot air temperature of 300 ° C. using a spun consisting of 48 nozzles, focused by a false twisting device using compressed air, and then put into a paper tube. A take-up package of 470 dt / 48 filament polyurethane elastic fibers was obtained.
- Example 1 and Example 1 except that a hydrocarbon mixture composed of the specific compound and a hydrocarbon compound other than the specific compound was appropriately contained so as to have the content of the specific compound and the area ratio of the hydrocarbon compound shown in Table 1 below. Polyurethane elastic fibers were obtained in the same manner.
- Comparative Example 2 Polyurethane elastic fibers were obtained in the same manner as in Comparative Example 1 except that the content of polydimethylsiloxane was changed to 1.0 wt%.
- Examples 13 to 20, Comparative Examples 8 to 12, which are methods for preparing a surface treatment agent for polyurethane elastic fibers A mixture of polydimethylsiloxane and a specific compound, a specific compound and a hydrocarbon compound other than the specific compound, or a hydrocarbon compound so as to have the content of the specific compound and the area ratio of the hydrocarbon compound shown in Table 2 below, or , A hydrocarbon compound other than the specific compound was appropriately mixed and mixed with a stirring blade at room temperature for 30 minutes to obtain a treatment agent for polyurethane elastic fibers.
- Examples 21 to 28 of polyurethane elastic fibers provided with a treatment agent for polyurethane elastic fibers, Comparative Examples 13 to 18 2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained. After cooling this to room temperature, dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution.
- a polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa ⁇ s (30 ° C.) was obtained.
- Table 3 shows. After applying the described amount and type of surface treatment agent to the polyurethane elastic fiber by nozzle oiling, the polyurethane elastic fiber was wound around a paper tube to obtain a winding package of the polyurethane elastic fiber of 470 dt / 48 filament.
- Example 29, Comparative Example 19 A winding package of 470 dt / 48 filament polyurethane elastic fibers was obtained in the same manner as in Examples 21 to 28 and Comparative Examples 13 to 18, except that the treatment agent for polyurethane elastic fibers was kneaded into the spinning stock solution instead of nozzle oiling. It was.
- the polyurethane elastic fiber containing a specific amount of a specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good detonability even if the content of silicone oil is small and having a small amount of multifilament single yarn variation. is there. Therefore, the polyurethane elastic fiber of the polyurethane elastic fiber according to the present invention can be suitably used for fabrics, sanitary material products and the like.
Abstract
Description
それらの問題を解決するために、シリコーンオイルからなる処理剤を糸に付与する方法が知られており、シリコーンオイルは高価であるため一般に安価な鉱物油を用いてシリコーンオイルを希釈して処理剤を調製して糸に付与される。しかし、シリコーンオイルを鉱物油等で希釈した処理剤では、コストダウンはできるものの、該処理剤を付与されたポリウレタン弾性繊維の巻糸体からの解舒性や摩擦性が低下してしまい、十分な解舒性、摩擦性が得られない。
[1]下記式(1):
[2]式中、n=3である前記式(1)で表される炭化水素化合物をポリウレタン弾性繊維重量に対して10ppm以上8000ppm以下で含有する、前記[1]に記載のポリウレタン弾性繊維。
[3]式中、nが2~5の整数である前記式(1)で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、前記[1]又は[2]に記載のポリウレタン弾性繊維。
[4]ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、トリアコンタンの保持時間より長い保持時間を占める成分の面積が5%未満である、前記[1]~[3]のいずれかに記載のポリウレタン弾性繊維。
[5]ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が5%未満である、前記[1]~[4]のいずれかに記載のポリウレタン弾性繊維。
[6]ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める成分の面積が5%未満である、前記[1]~[5]のいずれかに記載のポリウレタン弾性繊維。
[7]ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が20%未満である、前記[1]~[6]のいずれかに記載のポリウレタン弾性繊維。
[8]ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間を占める成分の面積が80%以上である、前記[1]~[7]のいずれかに記載のポリウレタン弾性繊維。
[9]前記[1]~[8]のいずれかに記載のポリウレタン弾性繊維を含む布帛。
[10]前記[1]~[8]のいずれかに記載のポリウレタン弾性繊維を含む衛生材料製品。
[11]下記式(1):
[12]式中、n=3である前記式(1)で表される炭化水素化合物を、0.10重量%以上20重量%以下で含有する、前記[11]に記載のポリウレタン弾性繊維用表面処理剤。
[13]式中、nが2~5の整数である前記式(1)で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、前記[11]又は[12]に記載のポリウレタン弾性繊維。
[14]ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうちトリアコンタンの保持時間より長い保持時間を占める成分の面積が5%未満である、前記[11]~[13]に記載のポリウレタン弾性繊維用表面処理剤。
[15]ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が5%未満である、前記[11]~[14]のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
[16]ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうちヘキサデカンの保持時間よりも短い保持時間を占める面積が5%未満である、前記[11]~[15]のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
[17]ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が20%未満である、前記[11]~[16]のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
[18]ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間に占める成分の面積が80%以上である、前記[11]~[17]のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
[19]シリコーンオイルを20重量%以上70重量%以下でさらに含有する、前記[11]~[18]のいずれかに記載のポリウレタン弾性繊維用表面処理剤。
前記特定化合物の含有量が10ppm未満であると、十分な解舒性向上効果を発揮することが難しく、より高い解舒性が得られるという観点からは30ppm以上であることが好ましい。他方、含有量が10000ppmを超えると、単糸バラけが発生しやすくなり、また、経時での解舒性が悪化する傾向がある。前記特定化合物の含有量の好ましい上限としては9000ppm以下であり、さらに好ましくは5000ppm以下である。
前記特定化合物のポリウレタン弾性繊維への含有の状態としては、前記特定化合物はポリウレタン弾性繊維の内部に含有していても、表面に付着していてもよい。また、前記特定化合物のポリウレタン弾性繊維への含有のさせ方としては、前記特定化合物又は前記特定化合物とそれ以外の炭化水素化合物からなる混合物を紡糸原液に直接練りこんでもよいし、前記特定化合物又は前記特定化合物とそれ以外の炭化水素化合物からなる混合物を表面処理剤に添加し糸表面に塗布する方法のいずれでも構わない。
尚、1の実施形態のポリウレタン弾性繊維では、式中、n=3である前記式(1)で表される炭化水素化合物をポリウレタン弾性繊維重量に対して10ppm以上8000ppm以下で含有することが好ましい。
また、他の実施形態であるポリウレタン弾性繊維用表面処理剤では、式中、n=3である前記式(1)で表される炭化水素化合物を、0.10重量%以上20重量%以下で含有することが好ましい。
また、単糸のバラけを抑制するためにアルコールとカルボン酸又はリン酸の縮合物からなるエステル化合物やリン酸エステル化合物を含有してもよい。エステル化合物やリン酸エステル化合物の好適な例としては、クエン酸トリメチルやアジピン酸ビス(2-エチルヘキシル)、安息香酸メチル、安息香酸ベンジル、ジ安息香酸ジエチレングリコール、ジ安息香酸ジプロピレングリコール、トリメット酸トリメチル、フタル酸ジブチル、リン酸トリクレジル、リン酸ジフェニル2-エチルヘキシル等が挙げられ、また、上記化合物のいずれか2つ以上を組み合わせて使用してもよい。
本実施形態のポリウレタン弾性繊維は、後述の方法にてヘキサンで抽出したGC/MSによって測定される前記特定化合物のピーク面積と前記特定化合物以外の炭化水素化合物のピーク面積の和で示される炭化水素化合物由来のピークの全面積のうち、保持時間が同条件で測定されるオクトコサンよりも長い成分の面積が5%未満であることがさらに好ましい。前記の炭化水素化合物由来のピークの全面積のうちオクトコサンの保持時間よりも保持時間の長い成分の面積が5%未満であると、式中、n=2~5である前記式(1)の特定化合物の流動性が良好となるため、式中、n=2~5である前記式(1)の特定化合物がポリウレタン弾性繊維の表面上にさらに局在化しやすくなり、解舒性をよりいっそう高めることができると考えている。オクトコサンの保持時間よりも保持時間の長い成分のより好ましい面積としては3%未満である。
また、単糸のバラけを抑制するためにアルコールとカルボン酸又はリン酸の縮合物からなるエステル化合物やリン酸エステル化合物を繊維用表面処理剤に含有してもよい。エステル化合物やリン酸エステル化合物の好適な例としては、クエン酸トリメチルやアジピン酸ビス(2-エチルヘキシル)、安息香酸メチル、安息香酸ベンジル、ジ安息香酸ジエチレングリコール、ジ安息香酸ジプロピレングリコール、トリメット酸トリメチル、フタル酸ジブチル、リン酸トリクレジル、リン酸ジフェニル2-エチルヘキシル等が挙げられ、また、上記化合物のいずれか2つ以上を組み合わせて使用してもよい。
2gに精秤したポリウレタン弾性繊維を50gのヘキサンに浸漬して10分間超音波をかけて抽出した後、エバポレータでヘキサンを留去した。その後、同じ容器にて抽出後のポリウレタン弾性繊維を再度50gのヘキサンに浸漬し、10分間超音波をかけて抽出した後、ポリウレタン弾性繊維を取り除き、エバポレータでヘキサンを留去することでヘキサンによる抽出物を得た。この抽出物の濃度が1600ppmとなるようヘキサンで希釈したサンプルを抽出液サンプルとして、GC/MS測定に供した。尚、抽出物の量が少ない場合は、ポリウレタン弾性繊維を適宜増量して同様の操作を行ってもよい。
詳細なGC/MSの条件は下記の通りであった。
装置 :Agilent 6890 GC, MSD-5973
カラム :DB-5MS (30m、0.25μm、ID 0.25mm)
オーブン:40℃(2分)-8℃/分―320℃(5分)
INJ/DET :325℃/325℃
ガス :ヘリウム
流量 :1.0ml/分
注入量 :1.0μl
注入方法:Split 10:1
前記(1)と同様にしてポリウレタン弾性繊維からの抽出物をGC/MSにて測定し、炭化水素化合物由来の全ピーク面積に対するトリアコンタンよりも保持時間の長い成分の面積をC30以上の成分の面積、オクトコサンよりも保持時間の長い成分の面積をC28以上の成分の面積、ヘキサデカンよりも保持時間の短い成分の面積をC16以下の成分の面積、オクタデカンよりも保持時間の短い成分の面積をC18以下の成分の面積、ヘキサデカンとトリアコンタンの保持時間の間に保持時間を有する成分の面積をC16-C30の成分の面積、オクタデカンとトリアコンタンの保持時間の間に保持時間を有する成分の面積をC18-C30の成分の面積、オクタデカンとオクトコサンの保持時間の間に保持時間を有する成分の面積をC18-C28の成分の面積としてそれぞれ百分率にて算出した。各面積の算出においてGC/MSにて炭化水素化合物由来ではない成分は除去して計算した。炭化水素化合物のピークは混合物の場合、ブロードに検出される場合があるため、その場合はピークの立ち上がり始めを始点とし、ピークの検出値が無視できるレベルまでなくなり始めた点を終点とし、始点と終点を直線で結んだベースラインから面積を算出した。
表面処理剤を1600ppmまでヘキサンで希釈し、前記(1)、(2)と同様に、表面処理剤中の各成分の値を算出した。尚、表面処理剤の混合前の原料を入手可能な場合は、測定をより簡易にするために炭化水素化合物そのものをヘキサンで1600ppmまで希釈して、前記(1)、(2)と同様に測定した。
紙管に巻幅60mmで総重量3kgになるように巻き取った後、ポリウレタン弾性繊維を20℃60%RHの環境に2日間静置した後、紙管から2cmのところまで糸を剥ぎ取って測定サンプルとし、測定サンプルの端面方向に15m/minで糸を消極解舒し、その時の張力を5分間測定し、その平均値を解舒張力とし、下記評価基準に従い7段階で判定した。解舒張力が低いほど、ポリウレタン弾性繊維がスムーズに解舒され、解舒時の糸切れが起こりにくいことが期待できる。ここでいう消極解舒とは、タテどり方式で解舒する方法のことをいう。
7:10g未満
6:10g以上13g未満
5:13g以上15g未満
4:15g以上25g未満
3:25g以上30g未満
2::30g以上35g未満
1:35g以上または糸切れ
長さ40mmのマルチフィラメントを10本平行に並ぶようにデマッチャー試験機にセットし、240mmの長さになるまで糸長方向に伸張し、再び元の40mmまで緩める伸張繰り返し操作を200rpmの速度で5000回行う。その後、図4に示すように、長さ40mmのマルチフィラメントを平らに置いた状態で、マルチフィラメント中の最も単糸が収束している部分からの距離が最大で0.5mm以上離れている単糸が発生した場合と単糸が切れた場合に単糸バラけが発生したとする。測定は同一サンプルあたり1組10本で5回測定を行い、合計50本の糸のうち何本バラけが発生したかをカウントし、発生率を計算し、下記7段階で評価した。単糸バラけ発生率が低いほど、ポリウレタン弾性繊維の使用時に単糸割れに由来する糸切れが起こりにくいことが期待できる。
7:発生率0%以上3%未満
6:発生率3%以上5%未満
5:発生率発生率5%未満
4:発生率5%以上10%未満
3:発生率10%以上15未満
2:発生率15%以上20%未満
1:発生率20%以上
[実施例1]
数平均分子量2000のポリテトラメチレンエーテルグリコール2000gと、4,4’-ジフェニルメタンジイソシアネート400gとを、乾燥窒素雰囲気化、60℃で3時間、撹拌下で反応させて、末端がイソシアネートでキャップされたポリウレタンプレポリマーを得た。これを室温まで冷却した後、ジメチルアセトアミドを加え、溶解してポリウレタンプレポリマー溶液とした。別途、エチレンジアミンとジエチルアミンを乾燥ジメチルアセトアミドに溶解したアミン溶液を作製し、ウレタンプレポリマー中のイソシアネート基とアミン溶液中のアミノ基の比率が1:1.03となるように添加し、10℃で冷却しながら反応させることで、ポリウレタン固形分濃度30質量%、粘度450Pa・s(30℃)のポリウレタン溶液を得た。
ポリウレタン固形分に対し、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)を1wt%、2-(2’-ヒドロキシ-3’-t-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾールを0.5wt%、および、25℃における動粘度が10mm2/sのポリジメチルシロキサンを糸重量に対して0.5wt%、式中、n=2~5である式(1)の特定化合物としてフィタン(n=3)を糸重量に対して50ppmになるように秤量し、ジメチルアセトアミドに溶解した後で、ポリウレタン溶液と混合して、均一な溶液とした後、室温、減圧下で脱泡し、これを紡糸原液とした。
この紡糸原液を、巻き取り速度500m/分、熱風温度300℃で、48個のノズルからなる紡口を用いて乾式紡糸し、圧縮空気による仮撚装置で集束した後、紙製の紙管に巻き取り、470dt/48フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。
以下の表1に示す特定化合物の含有量、炭化水素化合物の面積比率となるように、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素混合物を適宜含有させた以外は、実施例1と同様にしてポリウレタン弾性繊維を得た。
フィタン含有させない以外は、実施例1と同様にしてポリウレタン弾性繊維を得た。
ポリジメチルシロキサンの含有量を1.0wt%に変更した以外は、比較例1と同様にしてポリウレタン弾性繊維を得た。
以下の表1に示す、特定化合物の含有量、炭化水素化合物の面積比率となるように、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素混合物、特定化合物以外の炭化水素化合物を適宜含有させた以外は、実施例1と同様にしてポリウレタン弾性繊維を得た。
以下の表1に示すポリジメチルシロキサンの含有量となるようにした以外は、比較例4と同様にしてポリウレタン弾性繊維を得た。
以下の表2に示す、特定化合物の含有量、炭化水素化合物の面積比率となるように、ポリジメチルシロキサンと、特定化合物、特定化合物と特定化合物以外の炭化水素化合物からなる炭化水素の混合物、または、特定化合物以外の炭化水素化合物とを適宜混合し、室温で30分間攪拌羽にて混合して、ポリウレタン弾性繊維用処理剤を得た。
数平均分子量2000のポリテトラメチレンエーテルグリコール2000gと、4,4’-ジフェニルメタンジイソシアネート400gとを、乾燥窒素雰囲気化、60℃で3時間、撹拌下で反応させて、末端がイソシアネートでキャップされたポリウレタンプレポリマーを得た。これを室温まで冷却した後、ジメチルアセトアミドを加え、溶解してポリウレタンプレポリマー溶液とした。別途、エチレンジアミンとジエチルアミンを乾燥ジメチルアセトアミドに溶解したアミン溶液を作製し、ウレタンプレポリマー中のイソシアネート基とアミン溶液中のアミノ基の比率が1:1.03となるように添加し、10℃で冷却しながら反応させることで、ポリウレタン固形分濃度30質量%、粘度450Pa・s(30℃)のポリウレタン溶液を得た。
ポリウレタン固形分に対し、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)を1wt%、2-(2’-ヒドロキシ-3’-t-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾールを0.5wt%になるように秤量し、ジメチルアセトアミドに溶解した後で、ポリウレタン溶液と混合して、均一な溶液とした後、室温、減圧下で脱泡し、これを紡糸原液とした。
この紡糸原液を、巻き取り速度500m/分、熱風温度300℃で、真円形状の孔48個からなる紡口を用いて乾式紡糸し、圧縮空気による仮撚装置で集束した後、表3に記載した付与量と種類の表面処理剤をノズルオイリングにてポリウレタン弾性繊維に付与した後、紙製の紙管に巻き取り、470dt/48フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。
ポリウレタン弾性繊維用処理剤をノズルオイリングではなく、紡糸原液に練り込んだ以外は、実施例21~28、比較例13~18と同様に、470dt/48フィラメントのポリウレタン弾性繊維の巻き取りパッケージを得た。
Claims (19)
- 式中、n=3である前記式(1)で表される炭化水素化合物をポリウレタン弾性繊維重量に対して10ppm以上8000ppm以下で含有する、請求項1に記載のポリウレタン弾性繊維。
- 式中、nが2~5の整数である前記式(1)で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、請求項1又は2に記載のポリウレタン弾性繊維。
- ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、トリアコンタンの保持時間より長い保持時間を占める成分の面積が5%未満である、請求項1~3のいずれか1項に記載のポリウレタン弾性繊維。
- ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が5%未満である、請求項1~4のいずれか1項に記載のポリウレタン弾性繊維。
- ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める成分の面積が5%未満である、請求項1~5のいずれか1項に記載のポリウレタン弾性繊維。
- ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が20%未満である、請求項1~6のいずれか1項に記載のポリウレタン弾性繊維。
- ヘキサンによる抽出液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間を占める成分の面積が80%以上である、請求項1~7のいずれか1項に記載のポリウレタン弾性繊維。
- 請求項1~8のいずれか1項に記載のポリウレタン弾性繊維を含む布帛。
- 請求項1~8のいずれか1項に記載のポリウレタン弾性繊維を含む衛生材料製品。
- 式中、n=3である前記式(1)で表される炭化水素化合物を、0.10重量%以上20重量%以下で含有する、請求項11に記載のポリウレタン弾性繊維用表面処理剤。
- 式中、nが2~5の整数である前記式(1)で表される炭化水素化合物以外の炭化水素化合物をさらに含有する、請求項11又は12に記載のポリウレタン弾性繊維用表面処理剤。
- 前記ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうちトリアコンタンの保持時間より長い保持時間を占める成分の面積が5%未満である、請求項11~13のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
- 前記ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクトコサンの保持時間より長い保持時間を占める成分の面積が5%未満である、請求項11~14のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
- 前記ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、ヘキサデカンの保持時間よりも短い保持時間を占める面積が5%未満である、請求項11~15のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
- 前記ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンの保持時間よりも短い保持時間を占める面積が20%未満である、請求項11~16のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
- 前記ヘキサンに溶解した溶液のGC/MS測定において、炭化水素化合物由来のピークの全面積のうち、オクタデカンとオクトコサンの保持時間の間に占める成分の面積が80%以上である炭化水素化合物をさらに含有する、請求項11~17のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
- シリコーンオイルを20重量%以上70重量%以下でさらに含有する、請求項11~18のいずれか1項に記載のポリウレタン弾性繊維用表面処理剤。
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WO2023286651A1 (ja) * | 2021-07-13 | 2023-01-19 | 旭化成株式会社 | 熱可塑性ポリウレタン弾性繊維及びその巻糸体、該熱可塑性ポリウレタン弾性繊維を含むギャザー及び衛生材料、並びに該ポリウレタン弾性繊維の製造方法 |
JP7331296B1 (ja) | 2022-03-22 | 2023-08-22 | 松本油脂製薬株式会社 | 弾性繊維用処理剤及びその利用 |
WO2023181744A1 (ja) * | 2022-03-22 | 2023-09-28 | 松本油脂製薬株式会社 | 弾性繊維用処理剤及びその利用 |
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JP7065259B2 (ja) | 2022-05-11 |
CN113939618B (zh) | 2023-07-25 |
DE112020004306T5 (de) | 2022-06-30 |
JPWO2020250994A1 (ja) | 2021-12-09 |
SG11202112208UA (en) | 2021-12-30 |
CN113939618A (zh) | 2022-01-14 |
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