WO2011074622A1 - ポリウレタン弾性糸およびその製造方法 - Google Patents
ポリウレタン弾性糸およびその製造方法 Download PDFInfo
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- WO2011074622A1 WO2011074622A1 PCT/JP2010/072609 JP2010072609W WO2011074622A1 WO 2011074622 A1 WO2011074622 A1 WO 2011074622A1 JP 2010072609 W JP2010072609 W JP 2010072609W WO 2011074622 A1 WO2011074622 A1 WO 2011074622A1
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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
- D01F6/88—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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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- 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
Definitions
- the present invention relates to a polyurethane elastic yarn and a method for producing the same.
- Elastic fibers are widely used for stretch clothing and industrial materials such as leg wear, inner wear, and sports wear due to their excellent stretch properties.
- polyurethane elastic yarns are particularly frequently used, but polyurethane elastic yarns have a drawback that they are easily deteriorated or colored by light. For this reason, stretchable fiber products using polyurethane elastic yarns are gradually used by the light when they are displayed indoors, worn as clothes, and washed and dried outdoors. It becomes brittle.
- Patent Documents 1 and 2 a technology for producing polyurethane elastic yarn by spinning a spinning stock solution to which various ultraviolet absorbers are added together with polyurethane is known (Patent Documents 1 and 2). ).
- the added UV absorbers are specified to maintain excellent light resistance by preventing slipping off during washing, dry cleaning, etc. after friction, heat treatment, dyeing in textile processing, or textiles.
- Patent Document 3 There is also known a technique of copolymerizing a UV absorber of the above with polyurethane.
- the polyurethane elastic yarn just after spinning has the strength to break and recoverability of the polyurethane elastic yarn without adding an ultraviolet absorber. Compared to the above, it was the same at best, but it was lowered in some cases.
- the present invention improves light elongation as well as strong elongation characteristics (breaking strength, elongation at break) and recoverability, and ultraviolet rays after post-processing and washing during high-order processing.
- An object of the present invention is to provide a polyurethane elastic yarn and a method for producing the same, which can reduce the falling off of the absorbent.
- another object of the present invention is to provide a polyurethane elastic yarn capable of increasing the stress (hereinafter referred to as strength in the actual use region) when a strain is applied in the actual use region, and a method for producing the same.
- the polyurethane elastic yarn of the present invention employs any of the following means.
- a polyurethane elastic yarn comprising a polyurethane starting from a polymer diol and a diisocyanate, wherein the polyurethane contains at least one of the following (A), (B), and (C): Elastic yarn.
- (A) is contained, and (A) is a copolymer of a compound having a methacrylic acid skeleton and a compound having a benzotriazole skeleton and / or a compound having a benzophenone skeleton.
- the polyurethane elastic yarn according to (1) or (2) is a copolymer of a compound having a methacrylic acid skeleton and a compound having a benzotriazole skeleton and / or a compound having a benzophenone skeleton.
- the polyurethane elastic yarn according to (1) above, which contains (B), and the alkoxy group of (B) has 1 to 40 carbon atoms.
- An elastic yarn is produced by containing at least one of the following (A), (B), and (C) in a spinning dope containing a polyurethane starting from a polymer diol and a diisocyanate.
- a method for producing a polyurethane elastic yarn (A) Benzotriazole ultraviolet absorber containing one or more unsaturated bonds in the molecule and / or benzophenone ultraviolet absorber (B) Benzotriazole ultraviolet absorber containing one or more alkoxy groups in the molecule ( C) Benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule
- the polyurethane elastic yarn of the present invention has a high tensile elongation and a high recoverability by adding a specific ultraviolet absorber, as compared with a product containing no ultraviolet absorber or a product containing other ultraviolet absorbers, and It also has excellent light resistance.
- the UV absorber is less likely to fall off by post-processing or washing during high-order processing, and excellent light resistance can be maintained.
- the strength in the actual use area can be increased. Therefore, clothes using such elastic yarns are excellent in detachability, fit, wearing feeling, discoloration resistance, appearance quality, and the like, and can also be reduced in weight on a thin ground.
- the polyurethane in the present invention is not particularly limited as long as it is a polyurethane starting from a polymer diol and a diisocyanate. Also, the synthesis method is not particularly limited.
- it may be a polyurethane urea composed of a polymer diol, diisocyanate and a low molecular weight diamine, or may be a polyurethane composed of a polymer diol, diisocyanate and a low molecular weight diol.
- the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule
- Polyether diol, polyester diol, polycarbonate diol and the like are preferable as the polymer diol of the structural unit constituting the polyurethane.
- a polyether diol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.
- the polyether diol preferably contains a copolymerized diol compound containing a unit represented by the following general formula.
- polyether diol compound examples include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF).
- 3-methyl-THF as a modified PTMG THF and 2,3-dimethyl-THF as a modified PTMG, THF and neopentyl glycol as a modified PTMG, THF
- examples thereof include random copolymers in which ethylene oxide and / or propylene oxide are irregularly arranged.
- One kind of these polyether glycols may be used, or two or more kinds may be mixed or copolymerized.
- PTMG or modified PTMG is preferable.
- a mixture of butylene adipate, polycaprolactone diol, 3-methyl-1,5-pentanediol and polypropylene polyol is subjected to condensation polymerization with adipic acid or the like.
- the resulting dicarboxylic acid ester derived from a polyester glycol such as a polyester diol having a side chain, a dicarboxylic acid component consisting of 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid, and a diol component
- a polycarbonate diol containing units is preferably used.
- These polymer diols may be used alone, or may be used by mixing or copolymerizing two or more kinds.
- the molecular weight of the polymer diol used in the present invention is preferably 1000 to 8000, more preferably 1800 to 6000 in terms of number average molecular weight in order to obtain the desired level of elongation, strength, heat resistance and the like when formed into an elastic yarn. .
- a polymer diol having a molecular weight within this range an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be obtained.
- aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc.
- MDI diphenylmethane diisocyanate
- tolylene diisocyanate 1,4-diisocyanate benzene
- xylylene diisocyanate 1,4-diisocyanate
- 2,6-naphthalene diisocyanate 2,6-naphthalene diisocyanate
- alicyclic diisocyanate for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate Isocyanate, octahydro 1,5-naphthalene diisocyanate and the like are preferable.
- Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of polyurethane elastic yarns. 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 of the structural unit constituting the polyurethane.
- Preferred low molecular weight diamines include, for example, ethylenediamine (hereinafter abbreviated as EDA), 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylene.
- Examples include range amine, p, p′-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. It is also preferred that one or more of these are used. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to obtain a yarn excellent in elongation, elastic recovery, and heat resistance. 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.
- Low molecular weight diols include ethylene glycol (hereinafter abbreviated as EG), 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol. Etc. are representative. It is also preferred that one or more of these are used. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, a diol-extended polyurethane has a high heat resistance and a high strength yarn can be obtained. Furthermore, it is also preferable for the polyurethane in the present invention to use one or more end blockers.
- EG ethylene glycol
- 1,3 propanediol 1,4 butanediol
- bishydroxyethoxybenzene bishydroxyethylene terephthalate
- 1-methyl-1,2-ethanediol. Etc. are representative. It is also preferred that one or more
- monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, ethanol
- Monools such as propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.
- the molecular weight of the polyurethane is preferably in the range of 40000 to 150,000 as a number average molecular weight from the viewpoint of obtaining a fiber having high durability and strength.
- the molecular weight is measured by GPC and is a value converted by polystyrene.
- the melting point on the high temperature side is in the range of 150 ° C. or higher and 300 ° C. or lower.
- the melting point on the high temperature side corresponds to the melting point of so-called hard segment crystals of polyurethane or polyurethane urea as measured by DSC.
- PTMG having a molecular weight in the range of 1000 to 8000 as a polymer diol, MDI as a diisocyanate, ethylene glycol, 1,3 propanediol, 1,4 butanediol, ethylenediamine, 1,2-propanediamine, 1
- the elongation is high, and as described above, there are no practical problems including process passability and excellent heat resistance.
- the polyurethane elastic yarn of the present invention comprising the polyurethane as described above comprises (A) a benzotriazole-based UV absorber and / or a benzophenone-based UV absorber containing one or more unsaturated bonds in the molecule, and (B) in the molecule. Containing at least one of a benzotriazole-based ultraviolet absorber containing at least one alkoxy group, and (C) a benzophenone-based ultraviolet absorber containing at least one sulfonic acid group in the molecule It is.
- the benzotriazole ultraviolet absorber containing one or more unsaturated bonds in the molecule used in the present invention is a compound residue having an unsaturated bond with an aromatic hydrogen atom of an aromatic heterocyclic compound having a benzotriazole skeleton.
- a substituted compound there is no particular limitation as long as is a substituted compound, and examples thereof include a compound obtained by polymerizing a compound having an unsaturated bond as a monomer with a compound having a benzotriazole skeleton. In that case, only a compound having an unsaturated bond may be used as a monomer, or a copolymer containing other monomers may be used.
- a vinyl compound, an allyl compound, unsaturated carboxylic acid, etc. are preferable.
- UV absorbers include those having the structure shown in Chemical Formula 2.
- a copolymer of an unsaturated carboxylic acid compound such as an acrylic acid skeleton or a methacrylic acid skeleton and a compound having a benzotriazole skeleton is more preferable.
- a copolymer of a compound having a methacrylic acid skeleton and a compound having a benzotriazole skeleton is preferable from the viewpoint of stability of the spinning solution and spinning continuity.
- R (A) is a monovalent organic group containing one or more unsaturated bonds).
- the benzophenone ultraviolet absorber containing one or more unsaturated bonds in the molecule used in the present invention is a compound in which an aromatic hydrogen atom of an aromatic compound having a benzophenone skeleton is substituted with a compound residue having an unsaturated bond If it is, there will be no restriction
- ultraviolet absorbers include those having the structure shown in Chemical Formula 4.
- a copolymer of an unsaturated carboxylic acid-based compound such as an acrylic acid skeleton or a methacrylic acid skeleton and a compound having a benzophenone skeleton is more preferable from the viewpoint of strong elongation characteristics (breaking strength, breaking elongation) and recoverability.
- a copolymer of a compound having a methacrylic acid skeleton and a compound having a benzophenone skeleton is preferable from the viewpoints of removal of the ultraviolet absorber and stability of the spinning solution.
- R (A ′) is a monovalent organic group containing one or more unsaturated bonds).
- the benzotriazole ultraviolet absorber containing one or more alkoxy groups in the molecule used in the present invention is not particularly limited as long as it is a compound having a benzotriazole skeleton containing one or more alkoxy groups.
- the group having 1 to 40 carbon atoms, more preferably 1 to 35 carbon atoms, more preferably 1 to 24 carbon atoms, and most preferably 6 to 20 carbon atoms improves the strength and recovery properties. In view of this, it is also preferable from the viewpoint of spinnability. Further, it may contain other functional groups, may contain halogen from the viewpoint of compatibility with polyurethane, or may contain a plurality of benzotriazole skeletons. In particular, the structure shown in Chemical formula 6 is preferred.
- R (B) is a monovalent organic group, and X is a monovalent organic group or a halogen atom).
- the benzophenone ultraviolet absorber containing one or more sulfonic acid groups in the molecule used in the present invention is not particularly limited as long as it is a compound having a benzophenone skeleton containing one or more sulfonic acid groups. May partially contain salts such as sodium sulfonate and potassium sulfonate.
- a derivative of 2,4-dihydroxybenzophenonesulfonic acid is suitable for improving the strength and recovery properties, and may further contain other functional groups. It is highly effective to increase the stress when strain is applied in the actual use region of the yarn, and is preferable from the viewpoint of spinnability.
- the structure shown in Chemical formula 7 is preferred.
- R (C) is a monovalent organic group
- 2,4-dihydroxy-benzophenone sulfonic acid 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2-hydroxy-4-methoxy Mixture of sodium benzophenone-5-sulfonate, 2-hydroxy-4-methoxybenzophenone-6-sulfonic acid, 2-hydroxy-4-ethoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octyloxybenzophenone-5 Preferred are sulfonic acid, 2-hydroxy-4-octyloxybenzophenone-5-sulfonic acid, and the like.
- the amount of the ultraviolet absorber described above is preferably in the range of 0.5% by weight or more and less than 15% by weight with respect to the total weight of the polyurethane elastic yarn from the viewpoint of obtaining good processability and spinnability. From the viewpoint of reducing a decrease in chemical resistance, heat resistance and the like of the polyurethane elastic yarn, it is more preferably 0.5 wt% or more and 5 wt% or less with respect to the total weight of the polyurethane elastic yarn. In addition, it is also preferable that these contents are suitably determined by testing in advance according to the use.
- various stabilizers and pigments may be contained in the polyurethane elastic yarn or polyurethane spinning solution.
- hindered phenolic agents such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumilyzer GA-80” (product name) manufactured by Sumitomo Chemical Co., Ltd. are used as antioxidants.
- UV absorbers such as “Chinubin” (registered trademark) manufactured by Ciba Geigy Corporation, benzotriazole-based, benzophenone-based, benzoate-based, triazine-based drugs, “Sumilyzer P-16” manufactured by Sumitomo Chemical ”(Product name) and other phosphorus drugs, various hindered amine drugs, various inorganic pigments such as iron oxide, titanium oxide, and carbon black, fluorine or silicone resin powders, metal soaps such as magnesium stearate, Bactericides, deodorizers, lubricants such as silicone and mineral oil, barium sulfate containing silver, zinc and their compounds Cerium oxide, also contain various antistatic agents such as betaine and phosphoric acid preferably, It is also preferred to react the these with polymers. And it is also preferable to use a nitric oxide scavenger in order to further enhance the durability to light and various nitric oxides.
- UV absorbers such as “Chinubin”
- inorganic substances and inorganic porous materials such as bamboo charcoal, charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut husk activated carbon, coal-based activated carbon, zeolite, pearlite, etc.
- inorganic substances and inorganic porous materials such as bamboo charcoal, charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut husk activated carbon, coal-based activated carbon, zeolite, pearlite, etc.
- the spinning solution containing polyurethane is added to the following (A), (B), (C): It is characterized by containing at least one of them.
- Benzotriazole ultraviolet absorber containing one or more unsaturated bonds in the molecule and / or benzophenone ultraviolet absorber
- B Benzotriazole ultraviolet absorber containing one or more alkoxy groups in the molecule
- C Benzophenone ultraviolet absorber containing one or more sulfonic acid groups in the molecule
- a polyurethane solution is prepared in advance, It is preferable to add the ultraviolet absorber to the polyurethane solution.
- the method for producing a polyurethane solution and polyurethane as a solute in the solution may be either a melt polymerization method or a solution polymerization method, or may be another method.
- the solution polymerization method is more preferable.
- the solution polymerization method since the generation of foreign matters such as gel is small in the polyurethane, it is easy to spin and it is easy to produce a polyurethane elastic yarn having a low fineness. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.
- PTMG having a molecular weight of 1000 to 8000 is used as a polymer diol
- MDI is used as a diisocyanate
- ethylene glycol 1,3 propanediol
- 1,4 butane is used as a chain extender. It is synthesized using at least one of diol, ethylenediamine, 1,2-propanediamine, and 1,3-propanediamine, and has a high temperature melting point of 150 ° C. or higher and 300 ° C. or lower, more preferably 200 ° C. or higher. The thing of the range of 300 degrees C or less is mentioned.
- Such polyurethane can be obtained, for example, by synthesis using DMAc, DMF, DMSO, NMP, or the like, or a solvent containing these as a main component, using the above raw materials. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, a so-called one-shot method, or polymer diol and diisocyanate are first melt-reacted and then reacted.
- a particularly preferable method is a method in which a product is dissolved in a solvent and reacted with the above-mentioned diol to form polyurethane.
- the typical method for controlling the high temperature melting point of the polyurethane within the range of 150 ° C. to 300 ° C. is to control the type and ratio of the polymer diol, MDI, and diol.
- MDI polymer diol
- diol diol
- the molecular weight of the polymer diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively increasing the proportion of MDI.
- a polyurethane having a high melting point on the high temperature side can be obtained by relatively reducing the proportion of the polymer diol.
- amine catalyst examples include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-
- organometallic catalyst examples include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.
- the concentration of polyurethane in the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.
- the present invention it is preferable to add at least one of the above-mentioned (A) to (C) to the polyurethane solution.
- a method for adding the above-described ultraviolet absorbers (A) to (C) to the polyurethane solution any method can be adopted.
- a method using various means such as a method using a static mixer, a method using stirring, a method using a homomixer, a method using a biaxial extruder, etc. can be adopted.
- the above-mentioned ultraviolet absorbers (A) to (C) are preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.
- the addition of the ultraviolet absorbers (A) to (C) described above to the polyurethane solution causes a phenomenon in which the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the solution viscosity of the polyurethane before the addition.
- One or two end-capping agents such as monoamines such as butylamine and diamylamine, monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate It is also preferred to be used in the above mixed.
- the aforementioned agents such as light-resistant agents and antioxidants, pigments and the like may be added at the same time.
- the polyurethane elastic yarn of the present invention can be obtained by, for example, dry-spinning, wet-spinning, or melt-spinning and winding up the spinning stock solution configured as described above. Of these, dry spinning is preferred from the viewpoint of stable spinning at all finenesses from fine to thick.
- the fineness, the number of single yarns, the cross-sectional shape, etc. of the polyurethane elastic yarn of the present invention are not particularly limited.
- the yarn may be a monofilament composed of one single yarn or a multifilament composed of a plurality of single yarns.
- the cross-sectional shape of the yarn may be circular or flat.
- dry spinning method is not particularly limited, and spinning may be performed by appropriately selecting spinning conditions suitable for desired characteristics and spinning equipment.
- the permanent distortion rate and stress relaxation characteristics of the polyurethane elastic yarn of the present invention are particularly susceptible to the speed ratio of the godet roller and the winder, and therefore it is preferable to be appropriately determined according to the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic yarn having a desired permanent set rate and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is 1.15 to 1.65. And when obtaining a polyurethane elastic yarn having a particularly high permanent set rate and low stress relaxation, the speed ratio between the godet roller and the winder is more preferably in the range of 1.15 or more and 1.4 or less, and 1.15 or more. The range of 1.35 or less is more preferable.
- the speed ratio of the godet roller and the winder is 1.25 to 1.65.
- the range of 35 or more and 1.65 or less is more preferable.
- the strength of the polyurethane elastic yarn can be improved by increasing the spinning speed, it is preferable to adopt a spinning speed of 450 m / min or more in order to obtain a practically suitable strength level. Further, considering the point of industrial production, about 450 to 1000 m / min is preferable.
- a method for analyzing a benzotriazole-based ultraviolet absorber containing one or more unsaturated bonds in the molecule of the polyurethane elastic yarn in the present invention, the strength, elongation, permanent distortion rate of the polyurethane elastic yarn in the present invention A method of measuring stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in an organic solvent, and whiteness retention against light irradiation after immersion in an organic solvent will be described.
- the sample with a test length of 5 cm (L1) was subjected to 300% elongation at a tensile rate of 50 cm / min five times, and the stress at the fifth 300% elongation was defined as (G1).
- the length of the sample was maintained for 30 seconds with 300% elongation.
- the stress after holding for 30 seconds was defined as (G2).
- the length of the sample when the elongation of the sample was recovered and the stress became zero was defined as (L2). Furthermore, it extended until the sample cut
- the above characteristics are calculated by the following formula.
- the strain and stress at the time of recovery after holding for the 5th time for 30 seconds described above are plotted to draw a curve, and the stress at the time of 200% strain is (P-200), and in the stretch characteristic of a predetermined fineness (20 dtex). It was calculated as the intensity of the actual use area.
- the yarn was fixed in a 100% stretched state and subjected to UV exposure treatment.
- the UV exposure treatment was performed using a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. as a device at 63 ° C. and 60% RH. After this exposure treatment was performed twice in total, the yarn was left free for 24 hours at room temperature, and the breaking strength (G4) was measured by the same method as described above.
- the ratio (retention rate) of the breaking strength (G4) after the treatment to the breaking strength (G3) of the untreated yarn was defined as chemical resistance.
- Durability against light irradiation (%) 100 ⁇ (G4) / (G3) [Whiteness retention against light irradiation]
- the yarn was wound around a 5 ⁇ 5 cm sample plate with a minimum load (1.05 in terms of elongation) so fine that the influence of the color of the sample plate did not appear, and used as a sample.
- the UV exposure treatment was performed using a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. as a device at 63 ° C. and 60% RH. This exposure treatment was performed twice in total. The b value of the sample after the exposure treatment was measured to determine whiteness retention.
- b 7.0 (Y-0.847Z) / Y 1/2 (However, X, Y, Z were calculated according to JIS Z 8701: 1999) In the determination, b is less than 1.5, ⁇ , 1.5 or more and less than 3 is marked as ⁇ , 3 or more and less than 5 is marked as ⁇ , and 5 or more is marked as ⁇ .
- Example 1 A DMAC solution (35% by weight) of a polyurethane polymer comprising PTMG, MDI and ethylene glycol having a molecular weight of 2900 was polymerized by a conventional method to obtain a polymer solution P1.
- a polyurethane solution (“METACROL” (registered trademark) 2462, c1 manufactured by DuPont) produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), and , A condensation polymer of p-cresol and divinylbenzene (“Megachlor” (registered trademark) 2390, c2 manufactured by DuPont) was mixed 2 to 1 (weight ratio), and an antioxidant DMAc solution (concentration 35) was mixed. % By weight) and this was used as the other additive solution B1 (35% by weight).
- MEACROL polyurethane solution
- Polymer solution P1 benzotriazole ultraviolet absorber solution A1 containing one or more unsaturated bonds in the molecule, and other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively.
- Spinning solution D1 This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of godet roller and winder of 1.4, wound up, 20 dtex, monofilament, benzotriazole containing one or more unsaturated bonds in the molecule
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the breaking strength and breaking elongation are as follows: Comparative Example 1 (described later) containing no one or more unsaturated bonds in the molecule and a benzotriazole ultraviolet absorber containing no unsaturated bonds in the molecule Increased in comparison with Comparative Example 3 (described later).
- Example 2 As a benzotriazole ultraviolet absorber containing one or more unsaturated bonds in the molecule, 2- (2'-hydroxy-5'-methacryloxymethylphenyl) -2H-benzotriazole (compound of the above-mentioned chemical formula 3) is used.
- the DMAc solution was prepared in the same manner as in Example 1 except that it was used, and designated as DMAc solution A2 (35% by weight).
- the polymer solution P1 prepared in Example 1, the above-described ultraviolet absorber solution A2, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D2 and did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of godet roller and winder of 1.4, wound up, 20 dtex, monofilament, benzotriazole containing one or more unsaturated bonds in the molecule
- a polyurethane elastic yarn 200 g wound body having an ultraviolet absorber content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the breaking strength and breaking elongation are as follows: Comparative Example 1 (described later) containing no one or more unsaturated bonds in the molecule and a benzotriazole ultraviolet absorber containing no unsaturated bonds in the molecule Increased in comparison with Comparative Example 3 (described later).
- Example 3 A DMAc solution (35% by weight) of polyurethane urea polymer (P2) composed of PTMG, MDI, ethylenediamine having a molecular weight of 1800, and diethylamine as a terminal blocking agent was polymerized by a conventional method to obtain a polymer solution P2.
- P2 polyurethane urea polymer
- the DMAc solution P2, the ultraviolet absorbent solution A1 prepared in Example 1, and the other additive solution B1 were uniformly distributed at 94.0% by weight, 3.0% by weight, and 3.0% by weight, respectively.
- a spinning solution D3 This spinning solution D3 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 20 dtex, monofilament, benzoate containing one or more unsaturated bonds in the molecule.
- a polyurethane elastic yarn (500 g wound yarn) having a triazole ultraviolet absorber content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break is the comparative example 2 containing no benzotriazole-based UV absorber containing one or more unsaturated bonds in the molecule and the comparative example containing the benzotriazole UV absorber containing no unsaturated bonds in the molecule. Increased compared to 4 (described later).
- Example 4 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A2 prepared in Example 2, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D4.
- This spinning solution D4 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2 filament multifilament, one unsaturated bond in the molecule
- composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent was about 15% increase, but the durability after immersion in an organic solvent increased more than twice as compared with Comparative Example 4. did.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 1.
- Example 5 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A2 prepared in Example 2, and the other additive solution B1 prepared in Example 1 were 96.7% by weight, 0.3% by weight, It mixed uniformly by 0.0 weight%, and was set as the spinning solution D5.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break is the comparative example 2 containing no benzotriazole-based UV absorber containing one or more unsaturated bonds in the molecule and the comparative example containing the benzotriazole UV absorber containing no unsaturated bonds in the molecule. Increased compared to 4 (described later).
- Example 6 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A2 prepared in Example 2, and the other additive solution B1 prepared in Example 1 were 96.3% by weight, 0.7% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D6.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break is the comparative example 2 containing no benzotriazole-based UV absorber containing one or more unsaturated bonds in the molecule and the comparative example containing the benzotriazole UV absorber containing no unsaturated bonds in the molecule. Increased compared to 4 (described later).
- Example 7 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A2 prepared in Example 2, and the other additive solution B1 prepared in Example 1 were 84.0% by weight, 13.0% by weight, 3%, respectively. It mixed uniformly by 0.0 weight%, and was set as the spinning solution D7.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break is the comparative example 2 containing no benzotriazole-based UV absorber containing one or more unsaturated bonds in the molecule and the comparative example containing the benzotriazole UV absorber containing no unsaturated bonds in the molecule. Increased compared to 4 (described later).
- Example 8 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A2 prepared in Example 2, and the other additive solution B1 prepared in Example 1 were 80.0% by weight, 17.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D8.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 2 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break is the comparative example 2 containing no benzotriazole-based UV absorber containing one or more unsaturated bonds in the molecule and the comparative example containing the benzotriazole UV absorber containing no unsaturated bonds in the molecule. Increased compared to 4 (described later).
- Example 1 The polymer solution P1 prepared in Example 1 and the other additive solution B1 prepared in Example 1 were uniformly mixed at a ratio of 97% by weight and 3% by weight, respectively, to obtain a spinning solution E1.
- the spinning solution E1 was dry-spun at a spinning speed of 540 m / min with a speed ratio of the godet roller and the winder of 1.40, and wound to prepare a polyurethane elastic yarn of 20 dtex and monofilament.
- Example 2 The polymer solution P2 prepared in Example 3 and the other additive solution additive solution B1 prepared in Example 1 were uniformly mixed at a ratio of 97% by weight and 3% by weight, respectively, to obtain a spinning solution E2.
- the spinning solution E2 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn) was made.
- Table 2 shows durability and whiteness retention with respect to light irradiation.
- the breaking strength and breaking elongation were lower than those of Examples 3 to 5, and the permanent set rate and stress relaxation were higher than those of Examples 3 to 5, resulting in poor recoverability.
- Durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in an organic solvent, and whiteness retention against light irradiation were also significantly inferior to Examples 3-5. . Also, the color tone was inferior to Examples 3-5.
- This spinning solution E3 was dry-spun at a spinning speed of 540 m / min at a speed ratio of 1.4 between the godet roller and the winder, and wound to produce a 20 dtex monofilament polyurethane elastic yarn (200 g wound body).
- Table 2 shows durability and whiteness retention with respect to light irradiation.
- the breaking strength and breaking elongation were lower than those of Examples 1 and 2, and the permanent set rate and stress relaxation were higher than those of Examples 1 and 2, resulting in poor recoverability.
- the durability against light irradiation and the whiteness retention against light irradiation were improved as compared with Comparative Example 2 and were similar to Examples 1 and 2. However, the durability against light irradiation after immersion in an organic solvent and the whiteness against light irradiation were the same.
- the polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution C1 prepared in Comparative Example 3, and the other additive solution B1 prepared in Example 1 were 94% by weight, 3.0% by weight, and 3.0%, respectively.
- the mixture was uniformly mixed by weight% to obtain a spinning solution E3.
- This spinning solution E3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn) was made.
- Example 9 A DMAc solution was prepared in the same manner as in Example 1 except that 2-hydroxy-3-allyl-5-octylbenzophenone was used as a benzophenone-based ultraviolet absorber containing one or more unsaturated bonds in the molecule. DMAc solution A9 (35% by weight) was used.
- the polymer solution P1 prepared in Example 1, the UV absorber solution A9, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D9 and did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of godet roller and winder of 1.4, wound up, 20 decitex, monofilament, benzophenone-based UV containing one or more unsaturated bonds in the molecule
- a polyurethane elastic yarn 200 g wound yarn having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation. Break strength and elongation at break include Comparative Example 1 (noted above) containing no more than one unsaturated bond in the molecule and a benzophenone UV absorber containing no unsaturated bond in the molecule. Increased compared to Comparative Example 5 (described later). The values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 5, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 2 or more compared to Comparative Example 1.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to about twice or more compared to Comparative Examples 1 and 5.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 1, and when compared with Comparative Example 5, it is equivalent before immersion in an organic solvent. However, it improved after immersion in organic solvents.
- Example 10 The DMAc was prepared in the same manner as in Example 1 except that 2-hydroxy-5-methacryloxyethyl benzophenone (compound of formula 5) was used as the benzophenone-based ultraviolet absorber containing one or more unsaturated bonds in the molecule. A solution was prepared and used as DMAc solution A10 (35% by weight).
- the polymer solution P1 prepared in Example 1, the UV absorber solution A10, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D2 did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of godet roller and winder of 1.4, wound up, 20 decitex, monofilament, benzophenone-based UV containing one or more unsaturated bonds in the molecule
- a polyurethane elastic yarn 200 g wound yarn having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3. Breaking elongation, breaking strength, permanent distortion rate, strength in actual use area, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in an organic solvent Table 4 shows the whiteness retention with respect to light irradiation. Break strength and elongation at break include Comparative Example 1 (noted above) containing no more than one unsaturated bond in the molecule and a benzophenone UV absorber containing no unsaturated bond in the molecule. Increased compared to Comparative Example 5 (described later). The values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 5, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to about twice or more compared to Comparative Examples 1 and 5.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 1, and when compared with Comparative Example 5, it was equivalent before immersion in an organic solvent. However, it improved after immersion in organic solvents.
- Example 11 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A9 prepared in Example 9, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D11.
- This spinning solution D11 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 20 dtex, monofilament, benzophenone containing one or more unsaturated bonds in the molecule
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined in Comparative Example 2 in which one or more unsaturated bonds in the molecule were not added, and in Comparative Example 6 in which a benzophenone UV absorber not having an unsaturated bond was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 6, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent increased 1.5 times, and the durability after immersion in an organic solvent increased more than twice.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 2, and also when compared with Comparative Example 6.
- Example 12 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A10 prepared in Example 10, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D12.
- This spinning solution D12 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2 filaments multifilament, one unsaturated bond in the molecule
- composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent was an increase of about 40%, but the durability after immersion in an organic solvent increased more than twice.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 2, and also when compared with Comparative Example 6.
- Example 13 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A10 prepared in Example 10, and the other additive solution B1 prepared in Example 1 were 96.7% by weight, 0.3% by weight, It mixed uniformly by 0.0 weight%, and was set as the spinning solution D5.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 4. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined in Comparative Example 2 in which one or more unsaturated bonds in the molecule were not added, and in Comparative Example 6 in which a benzophenone UV absorber not having an unsaturated bond was contained in the molecule. Increased compared to below.
- Example 14 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A10 prepared in Example 10, and the other additive solution B1 prepared in Example 1 were 96.3% by weight, 0.7% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D14.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 4. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined in Comparative Example 2 in which one or more unsaturated bonds in the molecule were not added, and in Comparative Example 6 in which a benzophenone UV absorber not having an unsaturated bond was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 6, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersing the organic solvent was about 17%, but the durability after immersing the organic solvent increased more than twice.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 2 and improved as compared with Comparative Example 6.
- Example 15 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A10 prepared in Example 10, and the other additive solution B1 prepared in Example 1 were 84.0% by weight, 13.0% by weight, 3%, respectively. The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D15.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined in Comparative Example 2 in which one or more unsaturated bonds in the molecule were not added, and in Comparative Example 6 in which a benzophenone UV absorber not having an unsaturated bond was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 6, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent are significantly increased by about 3 times compared to Comparative Example 2, and when compared with Comparative Example 6, 1.5 times, respectively. Increased 6 times.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 2 and improved as compared with Comparative Example 6.
- Example 16 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A10 prepared in Example 10, and the other additive solution B1 prepared in Example 1 were 80.0% by weight, 17.0% by weight, It mixed uniformly by 0.0 weight%, and was set as the spinning solution D16.
- This spinning solution D16 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) was made.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 3. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 4 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined in Comparative Example 2 in which one or more unsaturated bonds in the molecule were not added, and in Comparative Example 6 in which a benzophenone UV absorber not having an unsaturated bond was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 4, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent are significantly increased by more than 3 times compared with Comparative Example 2, and are about 1.5 times and about 2.7 respectively compared with Comparative Example 6. Doubled.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 2 and improved as compared with Comparative Example 6.
- the polymer solution P1 prepared in Example 1, the UV absorber solution C1 described above, and the other additive solution B1 prepared in Example 1 were uniformly 94% by weight, 3.0% by weight, and 3.0% by weight, respectively.
- a spinning solution E3 This spinning solution E3 was dry-spun at a spinning speed of 540 m / min at a speed ratio of 1.4 between the godet roller and the winder, and wound to produce a 20 dtex monofilament polyurethane elastic yarn (200 g wound body).
- the polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution C1 prepared in Comparative Example 3, and the other additive solution B1 prepared in Example 1 were 94% by weight, 3.0% by weight, and 3.0%, respectively.
- the mixture was uniformly mixed by weight% to obtain a spinning solution E3.
- This spinning solution E3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn) was made.
- Example 17 Except for using 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole (the number of carbon atoms of the alkoxy group: 8) as a benzotriazole ultraviolet absorber containing one or more alkoxy groups in the molecule.
- the DMAc solution was prepared in the same manner as in Example 1 to obtain DMAc solution A17 (35% by weight).
- the polymer solution P1 prepared in Example 1, the UV absorber solution A17, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D17 and did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, 20 decitex, monofilament, benzotriazole-based ultraviolet ray containing one or more alkoxy groups in the molecule
- a polyurethane elastic yarn (200 g wound yarn) having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the breaking strength and elongation at break are the same as those of Comparative Example 1 (described above) in which one or more alkoxy groups are contained in the molecule but no benzotriazole ultraviolet absorber is blended, and the benzotriazole ultraviolet absorber that does not contain unsaturated bonds in the molecule Increased compared to the contained Comparative Example 7 (described later).
- the values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 7, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 2 or more compared to Comparative Example 1.
- the durability against light irradiation before immersion in an organic solvent was equivalent, but the durability after immersion in an organic solvent increased more than twice.
- the whiteness retention for light irradiation and the whiteness retention for light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 1, and are significantly improved after immersion in an organic solvent when compared with Comparative Example 7. It was.
- Example 18 2- (2'-hydroxy-4'-octadecyloxyphenyl) -5-chloro-benzotriazole (carbon number of alkoxy group: 18) as a benzotriazole ultraviolet absorber containing one or more alkoxy groups in the molecule
- the DMAc solution was prepared in the same manner as in Example 1 except that was used as DMAc solution A18 (35% by weight).
- the polymer solution P1 prepared in Example 1, the ultraviolet absorber solution A18, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D2 and did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, 20 decitex, monofilament, benzotriazole-based ultraviolet ray containing one or more alkoxy groups in the molecule
- a polyurethane elastic yarn (200 g wound yarn) having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, permanent distortion rate, strength in actual use area, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in an organic solvent Table 6 shows the whiteness retention with respect to light irradiation. Breaking strength and elongation at break include Comparative Example 1 (previously described) not containing a benzotriazole-based UV absorber containing one or more alkoxy groups in the molecule and a benzotriazole UV absorber containing no alkoxy groups in the molecule Increased compared to Comparative Example 7 (described later).
- the values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 7, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 2 or more compared to Comparative Example 1.
- the durability against light irradiation before immersion in an organic solvent was about 1.2 times, and the durability after immersion in an organic solvent was increased more than twice.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 1, and were significantly improved after immersion in an organic solvent when compared with Comparative Example 7. .
- Example 19 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A17 prepared in Example 17, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D19.
- This spinning solution D19 is dry-spun at a spinning speed of 600 m / min with a speed ratio of godet roller and winder of 1.20, wound up, 20 decitex, monofilament, benzotriazole containing one or more alkoxy groups in the molecule
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 in which a benzotriazole-based ultraviolet absorber containing at least one alkoxy group in the molecule was not blended and Comparative Example 8 in which a benzotriazole ultraviolet absorber not containing an alkoxy group was contained in the molecule. Increased compared to below.
- Example 20 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A18 prepared in Example 18, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D20.
- This spinning solution D20 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2 filaments multifilament, one or more alkoxy groups in the molecule
- composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in the organic solvent was equivalent, but the durability after immersion in the organic solvent increased more than twice.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 2, and when compared with Comparative Example 8, it is greatly improved after immersion in an organic solvent. It was done.
- Example 21 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A18 prepared in Example 18, and the other additive solution B1 prepared in Example 1 were 96.7% by weight, 0.3% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D21.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 in which a benzotriazole-based ultraviolet absorber containing at least one alkoxy group in the molecule was not blended and Comparative Example 8 in which a benzotriazole ultraviolet absorber not containing an alkoxy group was contained in the molecule. Increased compared to below.
- Example 22 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A18 prepared in Example 18, and the other additive solution B1 prepared in Example 1 were 96.3% by weight, 0.7% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D22.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, permanent distortion rate, strength in actual use area, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in an organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 in which a benzotriazole-based ultraviolet absorber containing at least one alkoxy group in the molecule was not blended and Comparative Example 8 in which a benzotriazole ultraviolet absorber not containing an alkoxy group was contained in the molecule. Increased compared to below.
- Example 23 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A18 prepared in Example 18, and the other additive solution B1 prepared in Example 1 were 84.0% by weight, 13.0% by weight, 3%, respectively. It mixed uniformly by 0.0 weight%, and was set as the spinning solution D23.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 in which a benzotriazole-based ultraviolet absorber containing at least one alkoxy group in the molecule was not blended and Comparative Example 8 in which a benzotriazole ultraviolet absorber not containing an alkoxy group was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 8, and the recoverability was improved.
- the durability against light irradiation and the durability after immersion in an organic solvent were about 2.8 times or more compared with Comparative Example 2, and increased significantly.
- the durability against light irradiation before immersion in an organic solvent was about 1.2 times, and the durability after immersion in an organic solvent was increased more than twice.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 2, and also when compared with Comparative Example 8, it is greatly improved after immersion in an organic solvent. It was.
- Example 24 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A18 prepared in Example 18, and the other additive solution B1 prepared in Example 1 were 80.0% by weight, 17.0% by weight, 3% The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D24.
- This spinning solution D24 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) was made.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 5. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 6 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 in which a benzotriazole-based ultraviolet absorber containing at least one alkoxy group in the molecule was not blended and Comparative Example 8 in which a benzotriazole ultraviolet absorber not containing an alkoxy group was contained in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 8, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 3 or more compared to Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent was about 1.2 times, and the durability after immersion in an organic solvent was increased to about 2.7.
- the whiteness retention for light irradiation and the whiteness retention for light irradiation after immersion in an organic solvent were also improved both before and after immersion in an organic solvent.
- the polymer solution P1 prepared in Example 1, the UV absorber solution C7 described above, and the other additive solution B1 prepared in Example 1 were uniformly 94% by weight, 3.0% by weight, and 3.0% by weight, respectively.
- a spinning solution E7 This spinning solution E7 was dry-spun at a spinning speed of 540 m / min at a speed ratio of 1.4 between the godet roller and the winder, and wound to prepare 20 dtex monofilament polyurethane elastic yarn (200 g wound body).
- Example 8 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution C7 prepared in Comparative Example 3, and the other additive solution B1 prepared in Example 1 were 94% by weight, 3.0% by weight, and 3.0%, respectively.
- the mixture was uniformly mixed by weight% to obtain a spinning solution E8.
- This spinning solution E8 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) Was made.
- Example 25 A DMAc solution was prepared in the same manner as in Example 1 except that 2,4-dihydroxy-benzophenonesulfonic acid was used as a benzophenone-based ultraviolet absorber containing one or more sulfonic acid groups in the molecule, and DMAc solution A25 (35% by weight).
- the polymer solution P1 prepared in Example 1, the UV absorber solution A25, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively. did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, 20 decitex, monofilament, benzophenone UV containing one or more sulfonic acid groups in the molecule
- a polyurethane elastic yarn (200 g wound yarn) having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation. Breaking strength and elongation at break include comparative example 1 (previously described) containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and a benzophenone UV absorber containing no sulfonic acid groups in the molecule Increased compared to Comparative Example 9 (described later).
- the values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 9, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 2 or more compared to Comparative Example 1.
- the durability against light irradiation before immersion in the organic solvent was equivalent, but the durability after immersion in the organic solvent increased more than twice.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared with Comparative Example 1, and were significantly improved after immersion in an organic solvent when compared with Comparative Example 9.
- Example 26 A DMAc solution was prepared in the same manner as in Example 1 except that 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid was used as a benzophenone-based ultraviolet absorber containing one or more sulfonic acid groups in the molecule. DMAc solution A26 (35% by weight).
- the polymer solution P1 prepared in Example 1, the UV absorber solution A26, and the other additive solution B1 were uniformly mixed at 94 wt%, 3 wt%, and 3 wt%, respectively, and the spinning solution D2 and did.
- This spinning solution is dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, 20 decitex, monofilament, benzophenone UV containing one or more sulfonic acid groups in the molecule
- a polyurethane elastic yarn (200 g wound yarn) having an absorbent content of 3% by weight was produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation. Breaking strength and elongation at break include comparative example 1 (previously described) containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and a benzophenone UV absorber containing no sulfonic acid groups in the molecule Increased compared to Comparative Example 9 (described later).
- the values of permanent set and stress relaxation were reduced as compared with Comparative Examples 1 and 9, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 2 or more compared to Comparative Example 1.
- the durability against light irradiation before immersion in the organic solvent was equivalent, but the durability after immersion in the organic solvent increased more than twice.
- the whiteness retention with respect to light irradiation and the whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 1, and when compared with Comparative Example 9, it is greatly improved after immersion in an organic solvent. It was.
- Example 27 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A25 prepared in Example 25, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D27.
- This spinning solution D27 is wound by dry spinning at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, 20 decitex, monofilament, benzophenone containing one or more sulfonic acid groups in the molecule
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone UV absorber containing no sulfonic acid groups in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 10, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased by a factor of 3 or more compared to Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent was about 1.2 times, and the durability after immersion in an organic solvent was increased more than twice.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared to Comparative Example 2, and were significantly improved after immersion in an organic solvent when compared with Comparative Example 10. .
- Example 28 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A26 prepared in Example 26, and the other additive solution B1 prepared in Example 1 were 94.0% by weight, 3.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D28.
- This spinning solution D28 was dry-spun at a spinning speed of 600 m / min with a speed ratio of a godet roller and a winder of 1.30, wound up, 20 dtex, 2-filament multifilament, one sulfonic acid group in the molecule
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone UV absorber containing no sulfonic acid groups in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 10, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in an organic solvent was 1.2 times, but the durability after immersion in an organic solvent increased more than twice as compared with Comparative Example 10. .
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared to Comparative Example 2, and were significantly improved after immersion in an organic solvent when compared with Comparative Example 10. .
- Example 29 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A26 prepared in Example 26, and the other additive solution B1 prepared in Example 1 were 96.7% by weight, 0.3% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D29.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone UV absorber containing no sulfonic acid groups in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 10, and the recoverability was improved.
- the durability against light irradiation and the durability against light irradiation after immersion in an organic solvent were significantly increased to more than twice as compared with Comparative Example 2.
- the durability against light irradiation before immersion in the organic solvent was about the same, but the durability after immersion in the organic solvent increased to about 1.8 times.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent were also significantly improved as compared to Comparative Example 2, and were significantly improved after immersion in an organic solvent when compared with Comparative Example 10. .
- Example 30 The polymer solution P2 prepared in Example 3, the ultraviolet absorbent solution A26 prepared in Example 26, and the other additive solution B1 prepared in Example 1 were 96.3% by weight, 0.7% by weight, It mixed uniformly by 0.0 weight%, and was set as the spinning solution D30.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone UV absorber containing no sulfonic acid groups in the molecule. Increased compared to below.
- Example 31 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A26 prepared in Example 26, and the other additive solution B1 prepared in Example 1 were 84.0% by weight, 13.0% by weight, 3%, respectively. It mixed uniformly by 0.0 weight%, and was set as the spinning solution D31.
- the spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, and 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn). Produced.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was as follows: Comparative Example 2 containing no benzophenone-based ultraviolet absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone ultraviolet absorber containing no unsaturated bond in the molecule. Increased compared to below.
- Example 32 The polymer solution P2 prepared in Example 3, the ultraviolet absorber solution A26 prepared in Example 26, and the other additive solution B1 prepared in Example 1 were 80.0% by weight, 17.0% by weight, The mixture was uniformly mixed at 0.0% by weight to obtain a spinning solution D32.
- This spinning solution D32 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) was made.
- the composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 7. Breaking elongation, breaking strength, strength in actual use area, permanent strain rate, stress relaxation, durability against light irradiation, whiteness retention against light irradiation, durability against light irradiation after immersion in organic solvent Table 8 shows the whiteness retention with respect to light irradiation.
- the tensile strength at break was determined by comparing Comparative Example 2 containing no benzophenone-based UV absorber containing one or more sulfonic acid groups in the molecule and Comparative Example 10 containing a benzophenone UV absorber containing no sulfonic acid groups in the molecule. Increased compared to below.
- the values of permanent set and stress relaxation were reduced as compared with Comparative Example 2 and Comparative Example 10, and the recoverability was improved.
- the durability after immersion in an organic solvent with respect to light irradiation was more than three times that of Comparative Example 2, which was significantly increased.
- the durability against light irradiation before immersion in an organic solvent was about 1.3 times, and the durability after immersion in an organic solvent was greatly increased to 2 times or more.
- Whiteness retention with respect to light irradiation and whiteness retention with respect to light irradiation after immersion in an organic solvent are also greatly improved as compared with Comparative Example 2, and also significantly improved after immersion in an organic solvent when compared with Comparative Example 10. It was.
- the polymer solution P1 prepared in Example 1, the above-described ultraviolet absorbent solution C9, and the other additive solution B1 prepared in Example 1 were uniformly 94% by weight, 3.0% by weight, and 3.0% by weight, respectively.
- a spinning solution E7 This spinning solution E7 was dry-spun at a spinning speed of 540 m / min at a speed ratio of 1.4 between the godet roller and the winder, and wound to prepare 20 dtex monofilament polyurethane elastic yarn (200 g wound body).
- the polyurethane elastic yarn of the present invention is excellent in high tensile elongation, high recoverability, and light resistance, and can maintain excellent light resistance without the removal of the UV absorber due to post-processing or washing during high-order processing. it can. Therefore, clothes using this elastic yarn have excellent detachability, fit, wear feeling, dyeing, discoloration resistance, appearance quality, and the like. In addition, because the strength in the actual use area is high, it is possible to reduce the fineness of the polyurethane fiber and design the fabric structure to reduce the content rate. Since the characteristics can be maintained, clothes using this elastic yarn are thin and light.
- the polyurethane elastic yarn of the present invention can be used not only alone but also in combination with various fibers to obtain an excellent stretch fabric, which can be used for knitting, weaving, and string processing.
- Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski trousers, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, gloves, various textile products, fastening materials, Further examples include fastening materials for preventing sanitary items such as paper diapers, waterproofing materials, imitation baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, and gaskets.
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Abstract
Description
(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ポリウレタン弾性糸であって、次の(A)、(B)、(C)のうちの少なくとも1種を含有することを特徴とするポリウレタン弾性糸。
(A)分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤および/またはベンゾフェノン系紫外線吸収剤
(B)分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤
(C)分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤
(2) 前記(A)を含有し、かつ、前記(A)が、不飽和カルボン酸系化合物とベンゾトリアゾール骨格を有する化合物および/またはベンゾフェノン骨格を有する化合物との共重合物であることを特徴とする、前記(1)に記載のポリウレタン弾性糸。
(3) 前記(A)を含有し、かつ、前記(A)が、メタクリル酸骨格を有する化合物とベンゾトリアゾール骨格を有する化合物および/またはベンゾフェノン骨格を有する化合物との共重合物であることを特徴とする、前記(1)または(2)に記載のポリウレタン弾性糸。
(4) 前記(B)を含有し、かつ、前記(B)のアルコキシ基が炭素数1から40であることを特徴とする、前記(1)に記載のポリウレタン弾性糸。
(5) 前記(B)のアルコキシ基が炭素数6から20であることを特徴とする、前記(4)に記載のポリウレタン弾性糸。
(6) 前記(C)を含有し、かつ、前記(C)がアルコキシ基を含有することを特徴とする、前記(1)に記載のポリウレタン弾性糸。
(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を含む紡糸原液に、次の(A)、(B)、(C)のうちの少なくとも1種を含有させて、弾性糸を製造することを特徴とするポリウレタン弾性糸の製造方法。
(A)分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤および/またはベンゾフェノン系紫外線吸収剤
(B)分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤
(C)分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤
このポリエーテル系ジオール化合物としては、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種以上混合もしくは共重合して使用してもよい。その中でもPTMGまたは変性PTMGが好ましい。
好ましい低分子量ジアミンとしては、例えば、エチレンジアミン(以下、EDAと略す)、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)フォ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も好ましい。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を失わない程度に加えてもよい。
さらに、本発明におけるポリウレタンには、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、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。
(A)分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤および/またはベンゾフェノン系紫外線吸収剤
(B)分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤
(C)分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤
これら(A)~(C)の系紫外線吸収剤を紡糸原液に含有させるにあたっては、予めポリウレタン溶液を作製しておき、その該ポリウレタン溶液に前記紫外線吸収剤を添加するのが好ましい。
糸試料約10mgをDMAcに10mlに溶解し、高速液体クロマトグラフィーにより分析を行った。高速液体クロマトグラフィーの検出器はUV検出器を使用し、測定波長340nmで測定した。定量には濃度の決定している上記(A)~(C)それぞれの紫外線吸収剤の溶液により検量線を予め作成し用いた。下記式により含有率を求めた。
含有率(重量%)=(糸試料ピーク面積/検量線ピーク面積)×検量線試料量/糸試料重量×100
[永久歪率、応力緩和、破断強度、破断伸度、実使用領域での強度]
インストロン4502型引張試験機を用い、ポリウレタン弾性糸を引張テストすることにより、永久歪率、応力緩和、破断強度、破断伸度を測定した。測定回数はn=3で測定し、それらの平均値を採用した。
応力緩和(%)=100×((G1)-(G2))/(G1)
永久歪率(%)=100×((L2)-(L1))/(L1)
破断伸度(%)=100×((L3)-(L1))/(L1)
また、前述の5回目の30秒間保持後の回復時における歪みと応力をプロットして曲線を描き、200%歪み時の応力を(P-200)として、所定の繊度(20dtex)の伸縮特性における実使用領域の強度として算出した。
糸を100%伸長状態で固定し、UV暴露処理を実施した。UV暴露処理は、機器としてスガ試験機社製のカーボンアーク型フェードメーターを用い、63℃、60%RHの温湿度で実施した。この暴露処理を合計2回実施した後、糸をフリーで24時間、室温で放置し、前記と同じ方法で破断強度(G4)を測定した。未処理糸の破断強度(G3)に対する、処理後の破断強度(G4)の割合(保持率)を耐薬品性とした。測定回数はn=3で測定し、それらの平均値を採用した。
[光照射に対する白度保持性]
糸を5×5cmの試料板に、試料板の色の影響が現れない程度に緻密に最小の荷重(伸長率で言えば1.05)で巻き取り、試料とし、これをUV暴露処理した。UV暴露処理は、機器としてスガ試験機社製のカーボンアーク型フェードメーターを用い、63℃、60%RHの温湿度で実施した。この暴露処理を合計2回実施した。暴露処理後の試料のb値を測定し、白度保持性を判定した。b値の測定は、JIS L 1013:1999のC法(ハンターの方法)に準じ、ハンター形色差計を用い、下記式に基づき算出した。測定回数は3回とし、その平均値を採用した。
b=7.0(Y-0.847Z)/Y1/2
(但し、X、Y、ZはJIS Z 8701:1999により算出した)
判定はbが1.5未満を◎、1.5以上3未満を○、3以上5未満を△、5以上を×と表記した。
ドライクリーニング等で使用されるテトラクロロエチレンに糸を約1時間浸漬した。その後、糸を取り出し、風乾してテトラクロロエチレンを除去した。その後、前述の光照射に対する耐久性と同法で耐久性(%)を算出した。
ドライクリーニング等で使用されるテトラクロロエチレンに糸を約1時間浸漬した。その後、糸を取り出し、風乾してテトラクロロエチレンを除去した。その後、前述の光照射に対する白度保持性と同法で白度保持性を測定した。
[実施例1]
分子量2900のPTMG、MDIおよびエチレングリコールからなるポリウレタン重合体のDMAC溶液(35重量%)を常法により重合し、ポリマ溶液P1とした。
分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤として、2 -( 2′- ヒドロキシ- 5' - メタクリロキシメチルフェニル)-2 H-ベンゾトリアゾール(前記化3の化合物)を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A2(35重量%)とした。
分子量1800のPTMG、MDI、エチレンジアミン、および末端封鎖剤としてジエチルアミンからなるポリウレタンウレア重合体(P2)のDMAc溶液(35重量%)を常法により重合し、ポリマ溶液P2とした。
実施例3で調整したポリマ溶液P2、実施例2で調製した紫外線吸収剤溶液A2、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D4とした。この紡糸溶液D4をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメント、分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例2で調製した紫外線吸収剤溶液A2、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.7重量%、0.3重量%、3.0重量%で均一に混合し、紡糸溶液D5とした。
実施例3で調整したポリマ溶液P2、実施例2で調製した紫外線吸収剤溶液A2、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.3重量%、0.7重量%、3.0重量%で均一に混合し、紡糸溶液D6とした。
実施例3で調整したポリマ溶液P2、実施例2で調製した紫外線吸収剤溶液A2、及び実施例1で調整したその他添加剤溶液B1を、それぞれ84.0重量%、13.0重量%、3.0重量%で均一に混合し、紡糸溶液D7とした。
実施例3で調整したポリマ溶液P2、実施例2で調製した紫外線吸収剤溶液A2、及び実施例1で調整したその他添加剤溶液B1を、それぞれ80.0重量%、17.0重量%、3.0重量%で均一に混合し、紡糸溶液D8とした。
実施例1で調整したポリマ溶液P1、及び実施例1で調整したその他添加剤溶液B1を、それぞれ、97重量%、3重量%の割合で均一混合し、紡糸溶液E1とした。この紡糸溶液E1をゴデローラーと巻取機の速度比を1.40として540m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、モノフィラメントのポリウレタン弾性糸を作製した。
実施例3で調整したポリマ溶液P2、及び実施例1で調整したその他添加剤溶液添加剤溶液B1を、それぞれ、97重量%、3重量%の割合で均一混合し、紡糸溶液E2とした。この紡糸溶液E2をゴデローラーと巻取機の速度比を1.20として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメントのポリウレタン弾性糸(500g巻糸体)を作製した。
[比較例3]
分子中に不飽和結合を含有しないベンゾトリアゾール系紫外線吸収剤である2-[2-ヒドロキシ-3,5-ビス(α, α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾールのDMAc溶液C1(35重量%)を調整した。
実施例1で調整したポリマ溶液P1、上記の紫外線吸収剤溶液C1、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液E3とした。この紡糸溶液E3をゴデローラーと巻取機の速度比1.4として540m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、モノフィラメントのポリウレタン弾性糸(200g巻糸体)を作製した。
[比較例4]
分子中に不飽和結合を含有しないベンゾトリアゾール系紫外線吸収剤である2-[2-ヒドロキシ-3,5-ビス(α, α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾールのDMAc溶液C1(35重量%)を調整した。
分子中に不飽和結合を一つ以上含有するベンゾフェノン系紫外線吸収剤として、2-ヒドロキシ-3-アリル-5-オクチルベンゾフェノンを用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A9(35重量%)とした。
分子中に不飽和結合を一つ以上含有するベンゾフェノン系紫外線吸収剤として、2-ヒドロキシ-5-メタクリロキシエチルベンゾフェノン(前記化5の化合物)を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A10(35重量%)とした。
実施例3で調整したポリマ溶液P2、実施例9で調製した紫外線吸収剤溶液A9、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D11とした。この紡糸溶液D11をゴデローラーと巻取機の速度比を1.20として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、モノフィラメント、分子中に不飽和結合を一つ以上含有するベンゾフェノン系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例10で調製した紫外線吸収剤溶液A10、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D12とした。この紡糸溶液D12をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメント、分子中に不飽和結合を一つ以上含有するベンゾフェノン系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例10で調製した紫外線吸収剤溶液A10、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.7重量%、0.3重量%、3.0重量%で均一に混合し、紡糸溶液D5とした。
実施例3で調整したポリマ溶液P2、実施例10で調製した紫外線吸収剤溶液A10、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.3重量%、0.7重量%、3.0重量%で均一に混合し、紡糸溶液D14とした。
実施例3で調整したポリマ溶液P2、実施例10で調製した紫外線吸収剤溶液A10、及び実施例1で調整したその他添加剤溶液B1を、それぞれ84.0重量%、13.0重量%、3.0重量%で均一に混合し、紡糸溶液D15とした。
実施例3で調整したポリマ溶液P2、実施例10で調製した紫外線吸収剤溶液A10、及び実施例1で調整したその他添加剤溶液B1を、それぞれ80.0重量%、17.0重量%、3.0重量%で均一に混合し、紡糸溶液D16とした。
分子中に不飽和結合を含有しないベンゾフェノン系紫外線吸収剤である2,4-ジヒドロキシベンゾフェノンのDMAc溶液C1(35重量%)を調整した。
分子中に不飽和結合を含有しないベンゾフェノン系紫外線吸収剤である2,4-ジヒドロキシベンゾフェノンのDMAc溶液C1(35重量%)を調整した。
分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤として、2-(2′-ヒドロキシ-4′-オクチルオキシフェニル)ベンゾトリアゾール(アルコキシ基の炭素数:8)を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A17(35重量%)とした。
分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤として、2-(2′-ヒドロキシ-4′-オクタデシルオキシフェニル)-5-クロロ-ベンゾトリアゾール(アルコキシ基の炭素数:18)を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A18(35重量%)とした。
実施例3で調整したポリマ溶液P2、実施例17で調製した紫外線吸収剤溶液A17、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D19とした。この紡糸溶液D19をゴデローラーと巻取機の速度比を1.20として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、モノフィラメント、分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例18で調製した紫外線吸収剤溶液A18、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D20とした。この紡糸溶液D20をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメント、分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例18で調製した紫外線吸収剤溶液A18、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.7重量%、0.3重量%、3.0重量%で均一に混合し、紡糸溶液D21とした。
実施例3で調整したポリマ溶液P2、実施例18で調製した紫外線吸収剤溶液A18、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.3重量%、0.7重量%、3.0重量%で均一に混合し、紡糸溶液D22とした。
実施例3で調整したポリマ溶液P2、実施例18で調製した紫外線吸収剤溶液A18、及び実施例1で調整したその他添加剤溶液B1を、それぞれ84.0重量%、13.0重量%、3.0重量%で均一に混合し、紡糸溶液D23とした。
実施例3で調整したポリマ溶液P2、実施例18で調製した紫外線吸収剤溶液A18、及び実施例1で調整したその他添加剤溶液B1を、それぞれ80.0重量%、17.0重量%、3.0重量%で均一に混合し、紡糸溶液D24とした。
分子中にアルコキシ基を含有しないベンゾトリアゾール系紫外線吸収剤である2-(2′-ヒドロキシ-4′-t-オクチルフェニル)ベンゾトリアゾールのDMAc溶液C7(35重量%)を調整した。
実施例3で調製したポリマ溶液P2、比較例3で調製した紫外線吸収剤溶液C7、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液E8とした。この紡糸溶液E8をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメントのポリウレタン弾性糸(500g巻糸体)を作製した。
分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤として、2,4-ジヒドロキシ-ベンゾフェノンスルホン酸を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A25(35重量%)とした。
分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤として、2-ヒドロキシ-4-メトキシベンゾフェノン-5-スルホン酸を用いた以外は実施例1と同じ方法でそのDMAc溶液を調製し、DMAc溶液A26(35重量%)とした。
実施例3で調整したポリマ溶液P2、実施例25で調製した紫外線吸収剤溶液A25、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D27とした。この紡糸溶液D27をゴデローラーと巻取機の速度比を1.20として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、モノフィラメント、分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例26で調製した紫外線吸収剤溶液A26、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94.0重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液D28とした。この紡糸溶液D28をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメント、分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤の含有量が3重量%であるポリウレタン弾性糸(500g巻糸体)を作製した。
実施例3で調整したポリマ溶液P2、実施例26で調製した紫外線吸収剤溶液A26、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.7重量%、0.3重量%、3.0重量%で均一に混合し、紡糸溶液D29とした。
実施例3で調整したポリマ溶液P2、実施例26で調製した紫外線吸収剤溶液A26、及び実施例1で調整したその他添加剤溶液B1を、それぞれ96.3重量%、0.7重量%、3.0重量%で均一に混合し、紡糸溶液D30とした。
実施例3で調整したポリマ溶液P2、実施例26で調製した紫外線吸収剤溶液A26、及び実施例1で調整したその他添加剤溶液B1を、それぞれ84.0重量%、13.0重量%、3.0重量%で均一に混合し、紡糸溶液D31とした。
実施例3で調整したポリマ溶液P2、実施例26で調製した紫外線吸収剤溶液A26、及び実施例1で調整したその他添加剤溶液B1を、それぞれ80.0重量%、17.0重量%、3.0重量%で均一に混合し、紡糸溶液D32とした。
光照射に対する有機溶剤浸漬後の耐久性は比較例2に比べて3倍以上となり、大幅に増加した。比較例10と比較した場合、有機溶剤浸漬前の光照射に対する耐久性は、1.3倍程度に、有機溶剤浸漬後の耐久性は2倍以上と大幅に増加した。光照射に対する白度保持性及び有機溶剤浸漬後の光照射に対する白度保持性も、比較例2に比べ大幅に改善し、比較例10と比べた場合も、有機溶剤浸漬後、大幅に改善された。
分子中にスルホン酸基を含有しないベンゾフェノン系紫外線吸収剤であるオクタベンゾンのDMAc溶液C9(35重量%)を調整した。
実施例3で調製したポリマ溶液P2、比較例9で調製した紫外線吸収剤溶液C9、及び実施例1で調整したその他添加剤溶液B1を、それぞれ94重量%、3.0重量%、3.0重量%で均一に混合し、紡糸溶液E10とした。この紡糸溶液E10をゴデローラーと巻取機の速度比を1.30として600m/分の紡糸速度で乾式紡糸して巻取り、20デシテックス、2フィラメントのマルチフィラメントのポリウレタン弾性糸(500g巻糸体)を作製した。
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ポリウレタン弾性糸であって、次の(A)、(B)、(C)のうちの少なくとも1種を含有することを特徴とするポリウレタン弾性糸。
(A)分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤および/またはベンゾフェノン系紫外線吸収剤
(B)分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤
(C)分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤 - 前記(A)を含有し、かつ、前記(A)が、不飽和カルボン酸系化合物とベンゾトリアゾール骨格を有する化合物および/またはベンゾフェノン骨格を有する化合物との共重合物であることを特徴とする、請求項1に記載のポリウレタン弾性糸。
- 前記(A)を含有し、かつ、前記(A)が、メタクリル酸骨格を有する化合物とベンゾトリアゾール骨格を有する化合物および/またはベンゾフェノン骨格を有する化合物との共重合物であることを特徴とする、請求項1または2に記載のポリウレタン弾性糸。
- 前記(B)を含有し、かつ、前記(B)のアルコキシ基が炭素数1から40であることを特徴とする、請求項1に記載のポリウレタン弾性糸。
- 前記(B)のアルコキシ基が炭素数6から20であることを特徴とする、請求項4に記載のポリウレタン弾性糸。
- 前記(C)を含有し、かつ、前記(C)がアルコキシ基を含有することを特徴とする、請求項1に記載のポリウレタン弾性糸。
- 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を含む紡糸原液に、次の(A)、(B)、(C)のうちの少なくとも1種を含有させて、弾性糸を製造することを特徴とするポリウレタン弾性糸の製造方法。
(A)分子中に不飽和結合を一つ以上含有するベンゾトリアゾール系紫外線吸収剤および/またはベンゾフェノン系紫外線吸収剤
(B)分子中にアルコキシ基を一つ以上含有するベンゾトリアゾール系紫外線吸収剤
(C)分子中にスルホン酸基を一つ以上含有するベンゾフェノン系紫外線吸収剤
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TWI656199B (zh) * | 2016-06-29 | 2019-04-11 | 臺灣永光化學工業股份有限公司 | 聚氨酯型高分子紫外線吸收劑 |
CN106917151B (zh) * | 2017-02-15 | 2020-07-17 | 杭州琪瑶纺织有限公司 | 一种紫外吸收面料 |
CN107602914B (zh) * | 2017-08-02 | 2019-08-13 | 合肥思敬齐化工材料有限责任公司 | 一种阴离子型防紫外线辐射的水溶性添加剂及其制备方法 |
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JP2022069010A (ja) | 2020-10-23 | 2022-05-11 | 東レ・オペロンテックス株式会社 | ポリウレタン弾性繊維およびその製造方法 |
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EP2514860A4 (en) | 2013-08-21 |
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