WO2010074015A1 - ポリマーアロイ繊維ならびに繊維構造体 - Google Patents
ポリマーアロイ繊維ならびに繊維構造体 Download PDFInfo
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- WO2010074015A1 WO2010074015A1 PCT/JP2009/071209 JP2009071209W WO2010074015A1 WO 2010074015 A1 WO2010074015 A1 WO 2010074015A1 JP 2009071209 W JP2009071209 W JP 2009071209W WO 2010074015 A1 WO2010074015 A1 WO 2010074015A1
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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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
- D01F6/92—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 polyesters
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23993—Composition of pile or adhesive
Definitions
- the present invention relates to a polymer alloy fiber in which a polylactic acid resin and a polyolefin resin are uniformly blended, and the polyolefin resin forms a sea component.
- plastics and fibers such as aliphatic polyester
- biodegradable plastics using biomass have not been used as general-purpose plastics because they have problems such as low mechanical properties and heat resistance and high production costs.
- polylactic acid using lactic acid obtained by fermentation of starch as a raw material has attracted attention as a biodegradable plastic having relatively high mechanical properties and heat resistance and low production cost.
- Polylactic acid-based resins typified by polylactic acid have been used for a long time in the medical field, for example, as surgical sutures, but recently, with the improvement of mass production technology, it has become possible to compete with other general-purpose plastics in terms of price. It was. For this reason, product development as a fiber has been activated.
- aliphatic polyester fibers such as polylactic acid
- agricultural materials and civil engineering materials that make use of biodegradability
- large-scale applications such as clothing, interiors such as curtains and carpets, and vehicle interiors.
- Applications to industrial and industrial materials are also expected.
- polypropylene is a resin that has recently been attracting attention.
- Polypropylene has a long life as a consumer good because it uses less energy per unit of production and has excellent durability.
- it has attracted attention as an environmentally friendly material because it has high mechanical properties, chemical resistance and dimensional stability in terms of performance, and has a very low specific gravity of 0.9 and light weight. The same is true for fibers, and the above properties are a strength and high competitiveness especially in material applications centering on nonwoven fabrics.
- aliphatic polyesters such as polylactic acid and polypropylene have the following problems, respectively, and their applications are limited.
- Patent Document 1 As a method for improving the abrasion resistance of polylactic acid, for example, methods for suppressing hydrolysis are disclosed (Patent Document 1 and Patent Document 2).
- the invention described in Patent Document 1 suppresses hydrolysis in the fiber production process by suppressing the water content of polylactic acid as much as possible.
- Patent Document 2 a monocarbodiimide compound is added. Fibers with improved hydrolysis resistance are disclosed.
- any fiber has a decrease in wear resistance in terms of suppressing the embrittlement of polylactic acid over time, none of them changes the property of polylactic acid “easy to fibrillate” It has been found that the initial wear resistance is no different from that of conventional products.
- polypropylene has high performance, it has a large back dust on polyester for fiber use.
- the reason is that the melting point is near 165 ° C., inferior to polyester (melting point of PET: 255 ° C.), and because it does not have a polar group, it cannot be dyed.
- Patent Document 7 and Patent Document 8 describe the use of an amine-modified elastomer as a compatibilizing agent for polylactic acid and polyolefin.
- the compatibility between the two components is dramatically improved, and the elongation as a molded product is dramatically improved, suggesting that it can be used for molded products such as door trims and pillar garnishes. ing.
- the stress at the time of elongating deformation after exiting the die was extremely high and could not be fiberized by melt spinning which requires a high draft.
- JP 2000-136435 A (page 4) JP 2001-261797 A (page 3) JP 2004-91968 A (pages 4-5) JP 2004-204406 A (pages 4 to 5) JP 2004-204407 A (pages 4 to 5) JP 2004-277931-A (pages 5-6) JP 2008-056743 A (pages 1 and 2) JP 2008-111043 (pages 1 and 2)
- the present invention solves the above-mentioned problems, and provides a polymer alloy fiber excellent in wear resistance, light weight, rebound, and aesthetic properties after dyeing, and a fiber structure composed of the fiber. Let it be an issue.
- the above-mentioned problem is a polymer alloy fiber made of a polymer alloy obtained by blending a polylactic acid resin (A), a polyolefin resin (B), and a compatibilizer (C), wherein the compatibilizer (C) Acrylic elastomer or styrene elastomer containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group
- the present invention it is possible to provide a synthetic fiber and a fiber structure that are remarkably improved in wear resistance and can provide a high-quality fiber structure, and that are optimal for general clothing use and industrial material use.
- the polylactic acid resin (A) referred to in the present invention is preferably crystalline.
- the polylactic acid is a polymer having — (O—CHCH 3 —CO) n — as a repeating unit, and refers to a polymer obtained by polymerizing an oligomer of lactic acid such as lactic acid or lactide.
- n represents the degree of polymerization and is preferably 800 to 8,000. Since lactic acid has two types of optical isomers, D-lactic acid and L-lactic acid, the polymer is also composed of poly (D-lactic acid) consisting only of D isomer and poly (L-lactic acid) consisting only of L isomer and There is polylactic acid consisting of both.
- the melting point is preferably 150 ° C. or higher and more preferably 160 ° C. in order to maintain the heat resistance of the fiber. More preferably, it is 170 degreeC or more, Most preferably, it is 180 degreeC or more.
- the two optical isomer polymers are blended and formed into a fiber, and then a high temperature of 140 ° C. or higher.
- a stereocomplex in which racemic crystals are formed by heat treatment is preferable because the melting point can be increased to 220 to 230 ° C.
- the polylactic acid resin (A) is a mixture of poly (L lactic acid) and poly (D lactic acid)
- the blend ratio is 40/60 to 60/40 to increase the ratio of stereocomplex crystals. Can be the best.
- stereocomplex crystals can also be formed by using polylactic acid of LD block copolymer consisting of both L lactic acid block and D lactic acid block. Can do. In this case, since the polymer becomes a single component, there is an advantage that the spinning equipment can be simplified.
- Crystal nucleating agents include talc, layered clay minerals, stearic acid, 12-hydroxystearic acid, stearic acid amide, oleic acid amide, erucic acid amide, methylene bis stearic acid amide, ethylene bis, which are highly compatible with polylactic acid.
- Stearic acid amide, ethylene bisoleic acid amide, butyl stearate, monoglyceride stearate, calcium stearate, zinc stearate, magnesium stearate, lead stearate and the like can be applied.
- the amount of residual lactide in the fiber is preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.05% by weight or less.
- the polylactic acid resin (A) may be one obtained by copolymerizing components other than lactic acid, for example, within a range that does not impair the properties of polylactic acid.
- the components to be copolymerized include polyalkylene ether glycols such as polyethylene glycol, aliphatic polyesters such as polybutylene succinate and polyglycolic acid, aromatic polyesters such as polyethylene isophthalate, and hydroxycarboxylic acids, lactones, dicarboxylic acids, and diols.
- An ester bond-forming monomer such as The copolymerization ratio of such a copolymer component is preferably 0.1 to 10 mol% with respect to polylactic acid, as long as the heat resistance deterioration due to the melting point drop is not impaired.
- the polylactic acid resin (A) further includes particles, matting agents, color pigments, crystal nucleating agents, flame retardants, plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, etc. as modifiers. It may be added.
- Color pigments include carbon black, titanium oxide, zinc oxide, barium sulfate, iron oxide, and other inorganic pigments, as well as cyanine, styrene, phthalocyanine, anthraquinone, perinone, isoindolinone, and quinophthalone.
- Organic pigments such as quinocridone and thioindigo can be used.
- modifiers such as various inorganic particles such as calcium carbonate, silica, silicon nitride, clay, talc, kaolin, and zirconium acid, and particles such as crosslinked polymer particles and various metal particles can also be used.
- waxes, silicone oils, various surfactants, various fluororesins, polyphenylene sulfides, polyamides, polyacrylates such as ethylene / acrylate copolymers, methyl methacrylate polymers, various rubbers, ionomers, polyurethanes And other polymers such as thermoplastic elastomers can be contained in small amounts.
- Examples of the lubricant preferably used for the polylactic acid resin (A) include fatty acid amides and / or fatty acid esters.
- Examples of the fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, methylol stearic acid amide, methylol behenic acid amide, dimethylol oil amide, dimethyl lauric acid amide, and dimethyl stearic acid.
- a compound having two amide bonds in one molecule such as amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, aromatic bisamide, etc., for example, methylene biscaprylic acid amide, methylene biscapric acid amide, methylene bislauric acid amide , Methylene bis myristic acid amide, methylene bis palmitic acid amide, methylene bis stearic acid amide, methylene bis isostearic acid amide, methylene bis behenic acid amide, methylene bis oleic acid amide, methyle Biserucic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bismyristic acid amide, ethylene bispalmitic acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bisbehe Ninamide, Ethylene bisoleic acid amide, Ethylene bis erucic
- N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl examples include oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide.
- the alkyl group may have a substituent such as a hydroxyl group introduced into its structure.
- methylol stearamide, methylol behenic acid amide, N-stearyl-12-hydroxystearic acid amide, N- Oleyl 12 hydroxystearic acid amide and the like are also included in the alkyl-substituted fatty acid monoamide of the present invention.
- fatty acid esters include lauric acid cetyl ester, lauric acid phenacyl ester, myristic acid cesyl ester, myristic acid phenacyl ester, palmitic acid isopropylidene ester, palmitic acid dodecyl ester, palmitic acid tetradodecyl ester, and palmitic acid pentadecyl ester.
- Aliphatic monocarboxylic acid esters such as ester, palmitic acid octadecyl ester, palmitic acid diarrheal ester, palmitic acid phenyl ester, palmitic acid phenacyl ester, stearic acid, diarrheal ester, behenic acid ethyl ester; monolauric acid glycol, monopalmitic acid Monoesters of ethylene glycol such as glycol and glycol monostearate, glycol dilaurate, glycodipalmitate Diesters of glycols such as glyceryl and distearate; monoesters of glycerin such as monolauric acid glycerin ester, monomyristylic acid glycerin ester, monopalmitic acid glycerin ester and monostearic acid glycerin ester; dilauric acid glycerin ester Glycerin diesters such as esters, glyceryl dipalmitate, g
- fatty acid bisamides and alkyl-substituted fatty acid monoamides are preferably used.
- Fatty acid bisamides and alkyl-substituted fatty acid monoamides are less reactive than amides of ordinary fatty acid monoamides, so that they do not easily react with polylactic acid during melt molding, and are also heat resistant due to their high molecular weight. It is high and does not sublime easily by melt molding, and exhibits excellent slipperiness without impairing the function as a lubricant.
- fatty acid bisamides can be used more preferably because the reactivity of amides is even lower, and ethylene bisstearic acid amide is more preferred.
- Two or more fatty acid amides and fatty acid esters may be used, or fatty acid amides and fatty acid esters may be used in combination.
- the content of the fatty acid amide and / or fatty acid ester is preferably 0.1% by weight or more based on the fiber weight in order to exhibit the above characteristics. Further, if the content is too large, the mechanical properties of the fiber may be lowered, or the color tone may be deteriorated when dyed with yellowishness, so the content is preferably 5% by weight or less.
- the content of the fatty acid amide and / or fatty acid ester is more preferably 0.2 to 4% by weight, still more preferably 0.3 to 3% by weight.
- the molecular weight of the polylactic acid resin (A) is more excellent in wear resistance as the viscosity ratio with the polyolefin resin (B) described later is higher, that is, the melt viscosity of the polylactic acid resin (A) is higher.
- the polylactic acid resin (A) preferably has a higher molecular weight, but if the molecular weight is too high, moldability and stretchability in melt spinning tend to be lowered.
- the weight average molecular weight is preferably 80,000 or more, more preferably 100,000 or more in order to maintain wear resistance. More preferably, it is 120,000 or more.
- the weight average molecular weight is preferably 350,000 or less, and more preferably 300,000 or less. More preferably, it is 250,000 or less.
- the weight average molecular weight is a value determined by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
- the production method preferably used for the polylactic acid-based resin (A) of the present invention is not particularly limited, and specifically, a direct dehydration condensation method in which lactic acid is dehydrated and condensed as it is in the presence of an organic solvent and a catalyst (Japanese Patent Laid-Open No. Hei 6). -65360), a method in which at least two homopolymers are copolymerized and transesterified in the presence of a polymerization catalyst (see JP-A-7-173266), and lactic acid is once dehydrated, An indirect polymerization method (see US Pat. No. 2,703,316) in which ring-opening polymerization is performed after the formation of a cyclic dimer is mentioned.
- polyolefin resin (B) used in the present invention examples include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, An unmodified olefin resin obtained by polymerizing or copolymerizing olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like, and olefin alcohols such as vinyl alcohol or derivatives thereof, A modified polyolefin resin modified with a compound such as a saturated carboxylic acid or a derivative thereof and a carboxylic acid vinyl ester is not included.
- Non-conjugated diene monomers such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1'-propenyl) -2-norbornene And a copolymer obtained by copolymerizing one or more of the above.
- the ethylene / ⁇ -olefin copolymer in the present invention is a copolymer of ethylene and at least one of ⁇ -olefins having 3 or more carbon atoms, preferably 3 to 20 carbon atoms.
- the 20 ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-
- ⁇ -olefins a copolymer using an ⁇ -olefin having 3 to 12 carbon atoms is preferable from the viewpoint of improving mechanical strength.
- the ethylene / ⁇ -olefin copolymer preferably has an ⁇ -olefin content of 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol%.
- the polyolefin resin (B) used for the polymer alloy fiber of the present invention is preferably a polyethylene resin, a polypropylene resin, or a poly-4-methyl-1-pentene resin from the viewpoint of easy control of the phase structure. A resin is more preferable.
- the production method preferably used for the polyolefin resin (B) of the present invention is not particularly limited, and a known method can be used.
- a known method can be used in the polyolefin resin.
- radical polymerization, Ziegler-Natta catalyst Coordination polymerization using anion, anionic polymerization, coordination polymerization using a metallocene catalyst, and the like can be used.
- the polyolefin resin (B) is a polypropylene resin
- High isotactic polypropylene resin is more preferred.
- stereoregularity isotacticity is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more.
- polypropylene resins having different stereoregularity may be used in combination.
- the highly isotactic polypropylene resin of the present invention is easily obtained by coordination polymerization using a Ziegler-Natta catalyst as a catalyst.
- the melting point of the polypropylene resin is preferably 150 ° C. or higher, and more preferably 160 ° C. in order to maintain the heat resistance of the polymer alloy fiber. More preferably, it is 170 degreeC or more.
- the melt viscosity of the polyolefin resin (B) is information that indirectly represents the molecular weight of the polymer. That is, if the melt viscosity is too low, the strength after fiberization becomes low, so a certain melt viscosity is required.
- the melt flow rate (MFR) serving as an index of the melt viscosity of the polyolefin resin (B) is 30 to 100 g / 10 min. It is preferably 50 to 90 g / 10 min.
- particles, crystal nucleating agents, flame retardants, antistatic agents, the above-mentioned lubricants preferably used for the polylactic acid resin (A), and the like may be added to the polyolefin resin (B).
- the presence or absence of crystallinity can be determined to be crystalline if the melting peak can be observed by differential scanning calorimetry (DSC) measurement. Further, the higher the crystallinity, the better the abrasion resistance, so that it is preferable, and the index can be determined by the amount of crystal melting peak heat in DSC.
- the crystal melting peak heat quantity ⁇ H is preferably 30 J / g, more preferably 40 J / g, and still more preferably 60 J / g.
- the crystal nucleating agent examples include talc.
- talc suitable for fibers talc having an average particle diameter of 5 ⁇ m or less and a particle diameter of 10 ⁇ m or more is based on the total amount of talc, while maintaining high mechanical properties of the fiber and exhibiting high crystallization characteristics. It is preferably 0 to 4.5% by volume or less.
- the particle diameter of talc is preferably 4 ⁇ m or less, and more preferably 3 ⁇ m or less. Most preferably, it is 1.5 ⁇ m or less.
- the lower limit of the average particle diameter of talc is not particularly limited, but it is preferably 0.2 ⁇ m or more because the agglomeration becomes higher and the dispersibility in the polymer becomes worse as the particle diameter becomes smaller.
- talc having a particle diameter of 10 ⁇ m or more is preferably 4.5% by volume or less based on the total amount of talc.
- the content of talc having a particle diameter exceeding 10 ⁇ m is more preferably 0 to 3% by volume, further preferably 0 to 2% by volume, and most preferably 0% by volume, based on the total amount of talc.
- the particle size of talc described in the above items (1) and (2) is a value obtained from a particle size distribution measured by a laser diffraction method using SALD-2000J manufactured by Shimadzu Corporation.
- sorbitol derivatives preferably used for the crystal nucleating agent include bisbenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (p-chlorobenzylidene) sorbitol, and bis (p-bromo).
- Benzylidene) sorbitol and sorbitol derivatives obtained by chemically modifying the sorbitol derivatives.
- phosphoric acid ester metal salt and the basic inorganic aluminum compound compounds described in JP-A No. 2003-192883 are preferably used.
- the melamine compound includes melamine, a substituted melamine compound in which the amino group hydrogen of melamine is substituted with an alkyl group, an alkenyl group, or a phenyl group (Japanese Patent Laid-Open No. 9-143238), and the amino group hydrogen of melamine is a hydroxyalkyl group.
- Substituted melamine compounds substituted with hydroxyalkyl (oxaalkyl) n group and aminoalkyl group Japanese Patent Laid-Open No. 5-202157
- deammonium condensation products of melamine such as melam, melem, melon, methone, benzoguanamine, acetoguanamine, etc.
- Guanamines can be used.
- organic acid salt and inorganic acid salt are mentioned as a melamine compound salt.
- organic acid salts include carboxylates such as isocyanurate, formic acid, acetic acid, oxalic acid, malonic acid, lactic acid and citric acid, and aromatic carboxylates such as benzoic acid, isophthalic acid and terephthalic acid. These organic acid salts may be used alone or in combination of two or more. Of these organic acid salts, melamine cyanurate is most preferred.
- Melamine cyanurate is surface-treated with a metal oxide sol such as silica, alumina or antimony oxide (JP-A-7-224049), or surface-treated with polyvinyl alcohol or cellulose ethers (JP-A-5-310716). And a surface treated with a nonionic surfactant of HLB 1 to 8 (JP-A-6-157820) can also be used.
- a metal oxide sol such as silica, alumina or antimony oxide
- a surface-treated with a nonionic surfactant of HLB 1 to 8 JP-A-6-157820
- the molar ratio of the melamine compound and the organic acid is not particularly limited, but it is preferable that the salt compound does not contain a free melamine compound or an organic acid that does not form a salt.
- the method for producing the organic acid salt of the melamine compound is not particularly limited, but in general, it can be obtained as a crystalline powder by mixing and reacting the melamine compound and the organic acid in water and then filtering or distilling the water and drying. it can.
- Inorganic acid salts include hydrochlorides, nitrates, sulfates, pyrosulfates, alkyl sulfonates such as methanesulfonic acid and ethanesulfonic acid, alkylbenzene sulfonates such as paratoluenesulfonic acid and dodecylbenzenesulfonic acid, and sulfamic acid.
- Salts phosphates, pyrophosphates, polyphosphates, phosphonates, phenylphosphonates, alkylphosphonates, phosphites, borates, tungstates and the like.
- inorganic acid salts melamine polyphosphate, melamine polyphosphate / melam / melem double salt, and paratoluenesulfonate are preferable.
- the molar ratio of the melamine compound and the inorganic acid is not particularly limited, but it is preferable that the salt compound does not contain a free melamine compound or an inorganic acid that does not form a salt.
- the method for producing the inorganic acid salt of the melamine compound is not particularly limited, but generally it can be obtained as a crystalline powder by mixing and reacting the melamine compound and the inorganic acid in water and then filtering or distilling the water and drying. it can. Further, methods for producing pyrophosphate and polyphosphate are described in, for example, US Pat. No. 3,920,796, JP-A-10-81691, JP-A-10-306081, and the like.
- the addition amount of the crystal nucleating agent has an inverse correlation with the mechanical properties of the fiber
- the addition amount is preferably 0.01 to 2% by weight based on the entire fiber. If the added amount is 0.01% by weight or more, the alloy is rapidly crystallized even in a short heat treatment in the fiber production process, so that a polymer alloy fiber excellent in fastness can be obtained. Moreover, by making the addition amount 2% by weight or less, it is possible to obtain a polymer alloy fiber excellent in fastness while suppressing a decrease in mechanical properties.
- the amount of the crystal nucleating agent added is more preferably 0.05 to 1.5% by weight, still more preferably 0.2 to 1% by weight.
- the compatibilizer (C) of the present invention is at least one selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group.
- the compatibilizer (C) is at least one selected from an acid anhydride group, an amino group, an imino group, and an epoxy group from the viewpoints of spinnability and wire diameter stability, strength, wear resistance, and heat resistance.
- the weight average molecular weight Mw of the compatibilizer (C) acts on the interface between the polylactic acid resin (A) and the polyolefin resin (B), and has a great influence on the interfacial peeling characteristics.
- a polymer having a molecular weight of 10,000 or more exhibits good interfacial delamination resistance, and by setting it to 350,000 or less, a polymer alloy having excellent spinnability is preferable. More preferably, it is a polymer.
- Mw is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
- the compatibilizing agent (C) of the present invention contains a (meth) acrylic ester vinyl unit or a styrene vinyl unit, preferably a (meth) acrylic ester vinyl unit or a styrene vinyl unit.
- a main component more preferably 60 wt% or more, more preferably 80 wt% or more, and other vinyl monomer component units excluding olefin monomers are preferably 40 wt% or less, More preferably, it may be a copolymer copolymerized by 20% by weight or less.
- styrene containing at least one functional group selected from an acid anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group
- a styrenic vinyl unit in terms of excellent controllability of the phase structure, excellent spinnability, strength, heat resistance and abrasion resistance (interfacial peel resistance). It is preferably 1 to 30% by weight, and more preferably 5 to 15% by weight.
- raw material monomer for forming the (meth) acrylic ester vinyl unit are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate.
- the raw material monomer for forming the styrene-based vinyl unit include styrene, ⁇ -methylstyrene, p-methylstyrene, ⁇ -methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, Examples thereof include 4-dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like. Among them, styrene and ⁇ -methylstyrene are preferably used. These may be used alone or in combination of two or more.
- the raw material monomer that forms the epoxy group-containing vinyl-based unit that is a constituent unit of the compatibilizer of the present invention include unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate Glycidyl esters of unsaturated polycarboxylic acids such as maleic acid and itaconic acid or unsaturated glycidyl ethers such as polyglycidyl ester, allyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4-glycidyl ether, etc. Can be mentioned.
- unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate
- Glycidyl esters of unsaturated polycarboxylic acids such as maleic acid and it
- glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.
- specific examples of the raw material monomer that forms an acid anhydride group-containing vinyl-based unit that is a constituent unit of the compatibilizer include maleic anhydride, itaconic anhydride, citraconic anhydride, or aconitic anhydride. Among them, maleic anhydride is preferably used. These may be used alone or in combination of two or more.
- examples of the raw material monomer that forms the unsaturated dicarboxylic acid unit serving as the carboxyl group-containing unit include maleic acid, maleic acid monoethyl ester, itaconic acid, and phthalic acid.
- maleic acid and itaconic acid are preferably used. Is done. These may be used alone or in combination of two or more. Two or more compatibilizers may be used in combination.
- melt viscosity of the compatibilizer (C) acts on the interface between the polylactic acid resin (A) and the polyolefin resin (B) to affect the melt viscosity of the entire polymer alloy and greatly affect the phase structure.
- the melt flow rate (MFR) is preferably higher than that of the polyolefin resin (B) to be used from the viewpoints of spinnability, strength, heat resistance, and wear resistance.
- an extremely high melt viscosity such that the MFR is less than 3 is not preferable because the melt viscosity of the entire polymer system is increased and the spinnability is deteriorated.
- a more preferred MFR is 5 to 20 g / 10 min.
- the epoxy value may be in the range of 0.1 to 10 meq / g for controlling the phase structure of the polymer alloy. Preferably, it is in the range of 1 to 7 meq / g, more preferably in the range of 2 to 5 meq / g. If the epoxy value is 0.1 meq / g or more, interfacial adhesion between the sea-island components is improved, and use of an epoxy value of 10 meq / g or less is preferable because gelation can be suppressed.
- the epoxy value is a value measured by the hydrochloric acid-dioxane method.
- the epoxy value of the polymer containing a glycidyl group-containing vinyl-based unit can be adjusted by adjusting the content of the glycidyl group-containing vinyl-based unit.
- the glass transition temperature of the compatibilizer (C) is preferably in the range of 30 to 100 ° C., more preferably in the range of 40 to 70 ° C. from the viewpoint of handleability.
- the glass transition temperature here is a value measured with a differential scanning calorimeter (DSC) in accordance with the method described in JIS K7121, and is the midpoint glass transition temperature when the temperature is raised at 10 ° C./min.
- the glass transition temperature of the compatibilizer (C) can be controlled by adjusting the composition of the copolymerization component.
- the glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing (meth) acrylic ester vinyl units such as butyl acrylate.
- the compatibilizing agent (C) of the present invention may use a sulfur compound as a chain transfer agent (molecular weight adjusting agent) in order to obtain a low molecular weight product.
- the polymer contains sulfur.
- sulfur since sulfur emits an unpleasant odor, it is preferable that the sulfur content is low.
- the sulfur atom is preferably 1000 ppm or less, and more preferably 100 ppm or less. Particularly preferably, it is 1 ppm or less.
- the method for producing the compatibilizing agent (C) of the present invention is not particularly limited as long as the conditions specified in the present invention are satisfied.
- Known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization Can be used.
- a polymerization initiator, a chain transfer agent and a solvent may be used, but these may remain as impurities in the finally obtained compatibilizer (C). . Since these impurities deteriorate heat resistance and light resistance, it is preferable that the amount of impurities is small.
- the amount of impurities is preferably 3% by weight or less, more preferably 1% by weight or less with respect to the polymer alloy fiber finally obtained.
- compatibilizing agent (C) when the compatibilizing agent (C) is produced, a method in which continuous bulk polymerization is performed in a short time of about 5 to 30 minutes at a high temperature of 150 ° C. or higher and a pressurized condition is preferable in order to achieve the above characteristics.
- compatibilizer (C) used in the present invention examples include “ARUFON” manufactured by Toagosei, “JONCRYL” manufactured by Johnson Polymer, “Clayton” manufactured by Clayton, “Tuftec” manufactured by Asahi Kasei Chemicals, “Dynalon” manufactured by JSR, etc. Is mentioned.
- the compatibilizer (C) by adding the compatibilizer (C), the affinity between the polylactic acid resin (A) and the polyolefin resin (B) is improved, and the phase structure is easily controlled.
- the phase structure of the polylactic acid resin (A) and the polyolefin resin (B) is stable, that is, the size distribution of the island component (polylactic acid resin) in the sea-island structure.
- the deformation ratio in the base of the polylactic acid resin (A) serving as an island component is minimized, and after the base is released. It is necessary to promote the relaxation of island components.
- the melt viscosity ⁇ A of the polylactic acid resin (A) and the melt of the polyolefin resin (B) a is from 1.3 to 10 viscosity ratio ( ⁇ a / ⁇ B) of the viscosity ⁇ B, (ii) the melt viscosity eta B of the polyolefin resin forming the sea component (B) is not more than 200 Pa ⁇ s Is preferred.
- the first condition (i) it is possible to reduce the storage energy in the mouthpiece hole and to suppress the deformation ratio of the polylactic acid resin forming the island to a smaller value.
- the “island domain deformation ratio” in the die hole there is a very close relationship between the “island domain deformation ratio” in the die hole and the spinnability.
- the “deformation ratio” is It becomes a very important factor.
- the blend ratio of the polylactic acid resin (A) and the polyolefin resin (B) is a sea-island polymer alloy in which the polylactic acid resin (A) is an island component and the polyolefin resin (B) is a sea component. Therefore, the total amount of the polylactic acid resin (A) and the polyolefin resin (B) is 100 parts by weight, and the polylactic acid resin (A) is 1 to 45 parts by weight, and the polyolefin resin (B) is 99 to 55. It is preferable to use parts by weight. More preferably, the ratio of the polylactic acid resin (A) is 10 to 40 parts by weight, still more preferably 15 to 35 parts by weight.
- the compatibilizing effect is exhibited by setting the compatibilizer (C) to 1 to 30 parts by weight with respect to the total amount (100 parts by weight) of the polylactic acid resin (A) and the polyolefin resin (B). In view of good fiber-forming properties, it is preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight.
- the polylactic acid resin is hardly exposed on the fiber surface (fiber side surface) of the polymer alloy fiber of the present invention.
- Polylactic acid-based resins and polyolefin-based resins are known to have almost no compatibility, and have low adhesive strength at the polymer alloy interface. For this reason, if the polylactic acid resin is exposed on the fiber surface, cracks start from the interface, and the fiber is easily fibrillated. The exposed state of the polylactic acid resin on the fiber surface is hardly distinguishable from the olefin resin portion even when observed with an optical microscope or the like.
- the fiber surface is etched with an alkaline solution to dissolve only the polylactic acid resin, and the degree of exposure is observed with an electron microscope (SEM). Can be captured.
- SEM electron microscope
- the area of the streaky crater is preferably 7% or less, and more preferably 5% or less.
- the streaky crater is a concave groove extending substantially parallel to the fiber axis direction (an angle within 10 ° with respect to the fiber axis) as shown in FIG.
- SEM observations of streaky craters can be captured with photographs that are usually magnified 5,000 times and, if necessary, 1,000 to 10,000 times.
- the area of the streak groove is the area of the streak groove that is captured at a viewing angle of 10 ⁇ m ⁇ 10 ⁇ m in the SEM observation image, and the area of all streak craters in the field of view using image analysis software “WinROOF”. It can be determined by measurement.
- the polymer alloy fiber obtained by combining the conventional polylactic acid resin (A), polyolefin resin (B), and compatibilizer (C) has a ballast effect just below the discharge hole due to the interfacial tension between the polymers. A bulge having a diameter several times the diameter of the discharge hole is generated. For this reason, thinning is likely to occur during the thinning deformation process during spinning, resulting in yarn breakage and a problem in quality such as yarn unevenness.
- the fiber of the present invention is a polymer combination design, that is, the optimum design of the polymer melt viscosity, the type of the compatibilizer, the viscosity, the die surface temperature and the die back pressure described later, the design of the die discharge linear velocity, etc.
- the filament or multifilament made of the polymer alloy fiber of the present invention preferably has a thread spot (Woster spot, U%, half Inert value) of 4% or less in order to suppress process passability and dyed spot after dyeing. 3% or less is more preferable. More preferably, it is 2% or less. Most preferably, it is 1.5% or less.
- the term “uniformly blended” refers to the following morphology. is there. That is, when a cross-sectional slice of the polymer alloy fiber is observed with a transmission electron microscope (TEM) (40,000 times), a continuous matrix component (gray portion) is formed as a sea component and a substantially circular shape as shown in FIG. Thus, a so-called sea-island structure is adopted in which the dispersed components (white and black) are used as island components.
- TEM transmission electron microscope
- the white portion is the polylactic acid resin (A)
- the black portion is the compatibilizer (C)
- the black and white two-layer structure is the polylactic acid resin (A) and the compatibilizer. It is a two-layer structure domain of (C).
- the domain size of the polylactic acid resin (A) constituting the island component is reduced to 0.005 to 2 ⁇ m in terms of diameter (the diameter converted from the domain area assuming that the domain is a circle). If so, the blended state becomes sufficiently uniform, which is preferable.
- the domain size of the island component within the above range, the abrasion resistance of the fiber can be dramatically improved.
- the adhesion with the polyolefin resin (B) constituting the sea component is improved because the stress concentration at the interface is dispersed as the domain size is smaller.
- the domain size is a certain size or less. There is a tendency for initial wear resistance to decrease. Therefore, the size of the island domain is more preferably 0.01 to 1.5 ⁇ m, and further preferably 0.02 to 1.0 ⁇ m.
- the domain diameter is further in a specific range. By covering the wavelength range of visible light (0.4 to 0.8 ⁇ m) and 1/5 wavelength (0.08 to 0.16 ⁇ m) of the wavelength, moderate light scattering inside the fiber is achieved. It is possible to provide a moist and lustrous gloss. In order to express a beautiful gloss, the domain diameter is preferably in the range of 0.08 to 0.8 ⁇ m.
- the domain size in the present invention is measured with respect to 100 domains per sample of drawn yarn as will be described later in the section G of the examples, and 10 values having the largest domain diameter and 10 values having the smallest domain diameter. This refers to 80 distributions excluding.
- the polymer alloy fiber of the present invention is different from a block copolymer in which polylactic acid blocks and polyolefin blocks are alternately present in one molecular chain, and the polylactic acid resin (A) and the polyolefin resin (B) are It is important that they exist substantially independently.
- the difference in this state is estimated by observing how much the melting point drop of the polyolefin resin before and after blending, that is, how much the melting point derived from the polyolefin resin in the polymer alloy falls from the melting point of the polyolefin resin before blending. be able to. If the melting point drop of the polyolefin resin is 3 ° C.
- the polylactic acid resin and the polyolefin are hardly copolymerized, and the polylactic acid molecular chain and the polyolefin molecular chain are substantially in a polymer alloy state.
- the fiber surface layer is a polyolefin resin that is substantially a sea component, the inherent properties of the polyolefin resin are reflected, and the wear resistance is dramatically improved. Therefore, in the present invention, the melting point drop of the blended polyolefin is preferably 2 ° C. or less.
- the polymer alloy fiber of the present invention is composed of a polymer alloy mainly composed of a polylactic acid resin (A) and a polyolefin resin (B), and the polylactic acid resin (A) has an island component.
- the polyolefin resin (B) forms a sea-island structure in which sea components are formed.
- the wear resistance is drastically improved and a high-quality gloss is exhibited.
- a catalyst having a relatively large molecular weight such as a metal stearate can be used alone or in combination for the purpose of preventing the heat resistance of the resin from being lowered due to the addition of the catalyst.
- the amount of the catalyst added is preferably 5 to 2000 ppm based on the synthetic fiber in order to control dispersibility and reactivity. More preferably, it is 10 to 1000 ppm, and further preferably 20 to 500 ppm.
- the polymer alloy fiber of the present invention preferably has a strength of 1 cN / dtex or more, more preferably 1.5 cN / dtex or more in order to keep the process passability and the mechanical strength of the product high. More preferably, it is 2 cN / dtex or more, and particularly preferably 3 cN / dtex or more.
- the polymer alloy fiber having such strength can be produced by melt spinning and drawing methods described later. Further, it is preferable that the elongation at break is 15 to 80% because the process passability is good when the fiber product is formed. More preferably, it is 20 to 70%, and further preferably 25 to 60%. In the category of the current industrial general-purpose process, it is extremely difficult to increase the strength of the polymer alloy fiber to 7 cN / dtex or more.
- the boiling water shrinkage of the polymer alloy fiber is 0 to 10%, it is preferable because the dimensional stability of the fiber and the fiber product is good. More preferably, it is 0 to 8%, further preferably 0 to 6%, and most preferably 0 to 4%.
- the polymer alloy fiber of the present invention is a multifilament, false twisted, or air jet stuffered to obtain a long-fiber crimped yarn.
- the crimped yarn comprising the polymer alloy fiber of the present invention is characterized by being excellent in crimp development and elastic recovery, being lightweight and excellent in heat retention.
- the crimp elongation rate after boiling water treatment is measured as the crimp property
- the crimp elongation rate can be adjusted in the range of 3 to 30%.
- the crimp elongation rate after the boiling water treatment is measured as follows.
- a crimped yarn unwound from a package (crimped yarn winding drum or bobbin) left in an atmosphere of an ambient temperature of 25 ⁇ 5 ° C. and a relative humidity of 60 ⁇ 10% for 20 hours or more is boiled for 30 minutes under no load. Immerse with. After the treatment, it is air-dried for 1 day and night (about 24 hours) in the above environment, and this is used as a sample of crimped yarn after the boiling water treatment. An initial load of 1.8 mg / dtex is applied to this sample, and after 30 seconds, marking is performed on a sample length of 50 cm (L1). Next, the sample length (L2) is measured after 30 seconds have elapsed by applying a measurement load of 90 mg / dtex instead of the initial load. And the crimp expansion
- required by the following Formula. Crimp elongation (%) [(L2-L1) / L1] ⁇ 100.
- the crimp elongation of the crimped yarn after boiling water treatment is 5% or more, for example, when it is made into a carpet or the like, it can be finished into a flexible and suitable material for spring and summer.
- the leveling property after dyeing is enhanced, and a volume material that exhibits a high-quality appearance can be obtained.
- the polymer alloy fiber of the present invention is excellent in durability such as strength retention and long-term appearance of the product in processing steps for forming a fabric structure such as dyeing and bulky processing, or in long-term use after making the product. Held over.
- the cross-sectional shape of the polymer alloy fiber of the present invention can be freely selected for a round cross-section, a hollow cross-section, a porous hollow cross-section, a multileaf cross-section such as a trilobal cross-section, a flat cross-section, a W cross-section, an X cross-section, and other irregular cross sections. It is possible.
- the degree of irregularity is more preferably in the range of 1.3 to 5.5, and further preferably in the range of 1.5 to 3.5.
- the form of the polymer alloy fiber of the present invention may be a monofilament composed of one long fiber or a multifilament, and the obtained polymer alloy fiber is cut into an appropriate length and treated as a short fiber. May be.
- the polymer alloy fiber of the present invention when used as a fiber structure, it can be applied to woven fabrics, knitted fabrics, non-woven fabrics, piles, cottons, etc., and may contain other fibers.
- it may be natural fiber, recycled fiber, semi-synthetic fiber, alignment with synthetic fiber, twisted yarn, mixed fiber.
- Other fibers include natural fibers such as cotton, hemp, wool, and silk, regenerated fibers such as rayon and cupra, semi-synthetic fibers such as acetate, nylon, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyacrylonitrile
- synthetic fibers such as polyvinyl chloride are applicable.
- the use of the fiber structure using the polymer alloy fiber of the present invention includes clothing that requires wear resistance, for example, sports such as outdoor wear, golf wear, athletic wear, ski wear, snowboard wear, and pants thereof.
- clothing that requires wear resistance
- women's and men's outerwear such as clothing, casual clothing such as blousons, coats, winter clothes and rainwear.
- materials such as uniforms and various covers, which can be preferably used.
- it can be used suitably for interior materials for automobiles, and among them, it is most suitable to be used for carpets for automobile interiors that require high wear resistance and moisture aging characteristics.
- the method for producing the polymer alloy fiber of the present invention is not particularly limited.
- the following method can be adopted using a direct spinning / drawing apparatus shown in FIG. That is, in the combination of the polylactic acid resin (A), the polyolefin resin (B), and the compatibilizer (C), the total amount of the polylactic acid resin (A) and the polyolefin resin (B) is 100 parts by weight.
- the ratio of the polylactic acid resin (A) is preferably 1 to 45 parts by weight, more preferably 10 to 45 parts by weight, still more preferably 15 to 40 parts by weight, and most preferably 20 to 35 parts by weight.
- the solubilizer (C) is preferably weighed and blended in an amount of preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, and still more preferably 5 to 10 parts by weight.
- the polylactic acid resin (A) that easily absorbs moisture is previously dried at 80 to 150 ° C. under vacuum or nitrogen, and after drying, is stocked in a moisture absorption prevention container or the like.
- the moisture absorption rate before melt spinning of the polylactic acid resin (A) is preferably 0.05% or less, more preferably 0.02% or less, and most preferably 0.008% or less.
- melt viscosity relationships of the polylactic acid resin (A), polyolefin resin (B), and compatibilizer (C), and the melt viscosity of the polyolefin resin (B) that forms the sea component Is important.
- a highly uniform alloy phase structure and a structure in which the polylactic acid resin (B) is hardly exposed on the fiber surface, and the domain size of the island component is 0.01. It is preferably ⁇ 2 ⁇ m.
- the following melt viscosity characteristics are preferable.
- the ratio ( ⁇ A / ⁇ B ) is preferably 1.3 to 10, and more preferably 1.8 to 9. More preferably, it is 3-8.
- the melt viscosity ⁇ B of the polyolefin resin (B) forming the sea component is preferably 200 Pa ⁇ s or less. More preferably, it is 150 Pa ⁇ s or less.
- the melt viscosity ⁇ C of the compatibilizer (C) is preferably higher than that of the polyolefin resin (B) that forms the sea component.
- the compatibilizer (C) effectively acts on the interface between the polylactic acid resin (A) and the polyolefin resin (B), and a smaller amount of compatibilizer can be used.
- the alloy phase structure becomes stable.
- a more preferable melt viscosity of the compatibilizer (C) is to make the melt viscosity satisfying ⁇ A > ⁇ C > ⁇ B.
- kneading using a uniaxial kneader, biaxial kneader, etc. once cooled and then chipped, or continuously in a molten state to a spinning device After feeding and weighing, melt spinning is performed to fiberize the polymer alloy.
- the addition timing of the compatibilizer (C) may be added in accordance with the kneading of the polylactic acid-based resin (A) and the polyolefin-based resin (B).
- the addition method is to supply the compatibilizer to the kneader as it is.
- the jacket temperature at the time of kneading in melt extrusion is preferably Tma + 5 ° C. to Tmb + 50 ° C. based on the melting point of the polylactic acid resin (A) (hereinafter referred to as Tma), and the shear rate is preferably 300 to 9800 sec ⁇ 1. .
- the jacket temperature and the shear rate are preferably low in order to suppress coloring of the resin, and more preferably Tma + 5 to 30 ° C.
- the spinning temperature is preferably as low as possible, and is preferably in the range of Tma + 30 ° C. to Tma + 70 ° C. A more preferable spinning temperature is Tma + 30 ° C. to Tma + 50 ° C.
- a high mesh filter layer (# 100 to # 200), porous metal, a non-woven filter with a small filter diameter (filter diameter 5) ⁇ 30 ⁇ m), an in-pack blend mixer (static mixer or high mixer) may be placed on the die.
- a multilayer filter made of a metal nonwoven fabric having a plurality of wire diameters is most effective for controlling the domain diameter.
- the thickness of the nonwoven fabric that is the core part of the multilayer filter is preferably 0.3 to 3 mm. Thickness increases the blending effect, but if the filter is too thick, filter tearing is likely to occur due to the pressure on the back of the filter, so 0.4 to 2 mm, more preferably 0.5 to 1 mm. is there.
- the polylactic acid resin (A) and the polyolefin resin (B) used in the present invention are incompatible polymers, a high interfacial tension acts on the blend interface, and the melt exhibits a very strong elastic behavior. Swelling due to the ballast effect occurs. For this reason, it is preferable to satisfy the following conditions in order to suppress the swelling of the yarn due to the ballast effect and to improve the spinning tone by stably stretching and thinning.
- the die surface temperature is set to 210 to 230 ° C.
- the pressure on the back surface of the base at the base surface temperature is set to 1 to 5 MPa.
- the average polymer flow rate in the die discharge hole is set to 0.03 to 0.30 m / sec.
- the base surface temperature aims to increase the molecular mobility of the polymer and promote relaxation of the island domain immediately after ejection. By setting it as said range, an island domain can relieve
- the pressure on the back surface of the die is a parameter having a correlation with the amount of elastic energy stored in the polymer in the die discharge hole. The lower the pressure at the back of the die, the smaller the elastic energy stored, so the polymer elongation flow becomes more stable. On the other hand, when the pressure at the back of the die is less than 1 MPa, the meterability of the discharge holes is lost and the discharge is unstable. become. Therefore, it is more preferably 1 to 4 MPa, and further preferably 1 to 3 MPa.
- the average polymer flow rate in the nozzle discharge hole is preferably 0.05 to 0.25 m / sec, more preferably 0.07 to 0.20 m / sec.
- the cooling start point of the spun yarn is preferably closer to the base surface, and it is preferable to start cooling from a position substantially 0.01 to 0.15 m vertically below the base surface.
- the cooling start point substantially vertically below is a horizontal line drawn from the upper end of the cooling air blowing surface and a vertical line b drawn downward from the base as shown in FIG.
- the cooling start point is more preferably 0.01 to 0.12 m substantially vertically downward from the die surface, and further preferably 0.01 to 0.08 m substantially vertically downward from the die surface.
- the cooling method may be a uniflow type chimney that cools from one direction, or an annular chimney that applies cooling air from the inside to the outside of the yarn or from the outside to the inside of the yarn, but preferably the inside of the yarn.
- An annular chimney that is cooled from the outside to the outside is preferable in that it can be uniformly and rapidly cooled.
- the substantially orthogonal direction means that the streamline of the cooling air is substantially perpendicular (inclination 70 to 110 °) to the line b as shown in FIG.
- the gas used for the cooling air there are no particular restrictions on the gas used for the cooling air, but rare gases such as argon and helium, nitrogen, or air that are stable at room temperature (very low reactivity), nitrogen, or air are preferably used. Nitrogen that can be used or air is particularly preferably used.
- the cooling air speed at this time is preferably 0.3 to 1 m / second, and more preferably 0.4 to 0.8 m / second.
- the temperature of the cooling air is preferably low in order to rapidly cool the yarn, but it is practically preferable to set the temperature to 15 to 25 ° C. in consideration of the cost of air conditioning.
- the sea-island structure of the present invention is formed by a specific polymer combination, and can be discharged without breaking the sea-island structure by controlling the spinning temperature, and further control of the discharge linear velocity at the die discharge hole, By controlling the cooling method and its conditions, the polymer alloy fiber of the present invention can be stably spun and taken out only for the first time.
- the spinning speed is 300 to 5000 m / min, and the film is wound once or continuously stretched.
- the polymer alloy fiber of the present invention is left in an unstretched state, orientation relaxation is likely to occur, and if there is a time difference until stretching between unstretched packages, the fiber easily exhibits variations in strength and heat shrinkage characteristics. Occurs. Therefore, it is preferable to employ a direct spinning / stretching method in which spinning and stretching are performed in one step.
- Stretching can be performed in one, two, or three stages. However, when the fiber of the present invention is subjected to high speed stretching, fiber diameter abnormalities (diameter spots in the fiber longitudinal direction) are likely to occur due to strain hardening. It is preferable to stretch in multiple stages. At this time, the first stage stretching is performed at a stretching temperature of 60 to 110 ° C. and a stretching ratio of 1.5 to 3 times, and the second and subsequent stages of stretching are performed at a stretching temperature of 80 to 140 ° C. and a stretching ratio of 1.1 to 3 It is preferable to carry out by doubling.
- the first heating roll is pulled at a spinning speed of 600 m / min, and then the first-stage stretching is performed between the first heating roll and the second heating roll.
- the 2nd heating roll peripheral speed at this time shall be 1800 m / min (3 times extending
- the peripheral speed of the third heating roll was 3240 m / min (the ratio between 2-3 heating rolls was 1.8 times), heat setting was performed at a third heating roll temperature of 140 ° C., and a fourth roll (non-heating roll, Winding around the package via a peripheral speed of 3200 m / min).
- the overall magnification may be set so that the obtained drawn yarn has an elongation of 15 to 80%.
- a false twisting device or an air jet stuffer device can be used for the bulk processing.
- the air jet stuffer device is a crimp processing device that is generally used for the production of crimped yarns for BCF carpets, and uses the turbulent flow effect of the air jet to form irregular tangle loops. It is the apparatus which provides the bulkiness of.
- GPC gel permeation chromatography
- Residual lactide amount of polylactic acid resin 1 g of a sample (polylactic acid resin) was dissolved in 20 ml of dichloromethane, and 5 ml of acetone was added to this solution. Furthermore, it was made to deposit with cyclohexane, it was made to precipitate, it analyzed by the liquid chromatograph using Shimadzu GC17A, and the amount of lactide was calculated
- the blend ratio of polylactic acid and polyolefin was determined in advance from a TEM image described later, and the lactide amount was determined by correcting the blend ratio.
- Carboxyl group end concentration A precisely weighed sample (polylactic acid-based resin extracted by the following method) was dissolved in o-cresol (water 5%), an appropriate amount of dichloromethane was added to this solution, and 0.02N KOH methanol solution was then added. Determined by titration with At this time, an oligomer such as lactide, which is a cyclic dimer of lactic acid, is hydrolyzed to generate a carboxyl group terminal, so that all of the carboxyl group terminal of the polymer, the monomer-derived carboxyl group terminal, and the oligomer-derived carboxyl group terminal are totaled. The carboxyl group terminal concentration was determined.
- the method for extracting the polylactic acid resin from the polymer alloy fiber is not particularly limited, but in the present invention, the polylactic acid resin is dissolved and filtered using chloroform to remove the polyolefin, and the filtrate is dried to extract. did.
- D. Polymer melting point and crystal melting calorie A temperature that gives an extreme value of a melting endothermic curve obtained by measuring 20 mg of a sample at a heating rate of 10 ° C / min using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer. The melting point (° C.) was used. Further, from the area surrounded by the peak forming the extreme value and the base line (crystal melting peak area), the heat of crystal melting ⁇ H (J / g) of the polymer was determined.
- the blend ratio of the polylactic acid resin (A) and the polyolefin resin (B) in the fiber is corrected by the cross-sectional area ratio obtained from the TEM image (5.93 ⁇ 4.65 ⁇ m) by the specific gravity of each component. And obtained as a weight ratio.
- polylactic acid: 1.24 and polyolefin: 0.91 were used for the specific gravity of each component in this example.
- TEM apparatus Hitachi H-7100FA type, conditions: acceleration voltage 100 kV.
- Fineness A 100-meter yarn was measured in a skein shape with a measuring scale, the weight of the 100-meter yarn was measured, and the weight was multiplied by 100 to obtain the fineness (dtex). The measurement was performed three times, and the average value was defined as the fineness (dtex).
- Boiling water shrinkage (boiling yield) The sample yarn was immersed in boiling water for 15 minutes, and obtained from the following equation from the dimensional change before and after immersion.
- Boiling water shrinkage (%) [(L 0 ⁇ L 1 ) / L 0 ] ⁇ 100
- L 0 skein length obtained by scraping the sample and measuring it under an initial load of 0.088 cN / dtex.
- L 1 The skein obtained by measuring L 0 was treated with boiling water in an unloaded state and air-dried, and then the initial load was 0.088. Skein length measured under cN / dtex.
- Crimp elongation rate A crimped yarn unwound from a package (crimped yarn winding drum or bobbin) that has been left in an atmosphere with an ambient temperature of 25 ⁇ 5 ° C and a relative humidity of 60 ⁇ 10% for more than 20 hours. Immerse with boiling water for 30 minutes. After the treatment, it is air-dried for 1 day and night (about 24 hours) in the above environment, and this is used as a sample of crimped yarn after the boiling water treatment. An initial load of 1.8 mg / dtex is applied to this sample, and after 30 seconds, marking is performed on a sample length of 50 cm (L1).
- the sample length (L2) is measured after 30 seconds have elapsed by applying a measurement load of 90 mg / dtex instead of the initial load.
- extension rate (%) after a boiling water process is calculated
- Crimp elongation (%) [(L2-L1) / L1] ⁇ 100.
- the average particle diameter D50 of the crystal nucleating agent and the content of the crystal nucleating agent of 10 ⁇ m or more was measured by a laser diffraction method using SALD-2000J manufactured by Shimadzu Corporation. Moreover, the volume% of the crystal nucleating agent of 10 ⁇ m or more was determined from the obtained particle size distribution.
- Abrasion resistance of carpet After twisting the crimped yarn with two S twists and Z twists, and twisting the twisted yarn into a PP spunbonded nonwoven fabric as the front yarn, a backing material is applied to the back of the base fabric and dried. A tufting carpet was obtained (weighing 1200 g / m 2 ). The tufting carpet was cut into a circular shape having a diameter of 120 mm, and a 6 mm hole was formed in the center to obtain a test piece.
- the test piece After measuring the weight W 0 of the test piece, the test piece was attached to a Taber abrasion tester (Rotary Abster) defined in ASTM D 1175 (1994) with the surface facing up, H # 18 abrasion rod, compression load 1 kgf (9. 8N), the sample holder rotation speed 70 rpm, perform wear test wear times 5500 times were measured sample weight W 1 after the wear test.
- the wear weight loss rate was calculated using these measured values and the following equation.
- Abrasion weight loss rate (%) (W 0 ⁇ W 1 ) ⁇ 100 / (W 2 ⁇ A 1 / A 0 )
- W 0 Weight of circular carpet before measurement
- W 1 Weight of the circular carpet after measurement
- W 2 basis weight of the carpet (g / m 2 )
- a 0 Total area of circular carpet (m 2 )
- a 1 Total area (m 2 ) of the portion where the wear wheel contacts.
- C1 Amino group-modified SEBS (JSR “Dynalon” 8630P, styrene content 15% by weight, MFR 15 g / 10 min (230 ° C., 21.2 N))
- C2 Imine group-modified SEBS (“Tough Tech” N503, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene content 30% by weight, MFR 20 g / 10 min (230 ° C., 21.2 N))
- C3 Maleic anhydride-modified SEBS (Clayton “Clayton” FG1924, styrene content 13% by weight, maleic anhydride content 1% by weight, MFR 11 g / 10 min (230 ° C., 21.2 N))
- Example 1 Polylactic acid P1 (melting point 177 ° C., melt viscosity 770 Pa ⁇ s) as polylactic acid resin (A), O1 as polyolefin resin (B), 30 parts by weight as C1 (melt viscosity 555 Pa ⁇ s) as a compatibilizer, A hopper 1 of a spinning device equipped with a biaxial kneader (two axes in the same direction, shaft diameter 20 mm, L / D45) shown in FIG. 3 that is chip-blended at a ratio of 70 parts by weight and 5 parts by weight (total of 105 parts by weight). Was charged. The polylactic acid resin (A) was dried at 110 ° C.
- the moisture content was adjusted to 80 ppm.
- the jacket temperature of the twin screw extrusion kneader 2 set to 200 ° C. and the shaft rotation speed at the time of kneading set to 300 rpm, the molten polymer is guided to the spinning block 3 kept at a temperature of 230 ° C., and further metered and discharged by a gear pump.
- the molten polymer was introduced into the built-in spin pack 4 and spun from the spinneret 5.
- a SUS nonwoven fabric filter (nonwoven fabric thickness: 0.6 mm) having an absolute filtration diameter of 10 ⁇ m was incorporated directly above the spin pack base.
- a round hole having a diameter of 0.9 mm and a hole depth of 6.3 mm was used as the die.
- the base surface temperature was 223 ° C.
- An annular chimney 6 (cooling length 30 cm) is installed so that the upper end of the blow hole comes to a position 5 cm below the base surface, and the yarn 7 is cooled and solidified at a cooling air temperature of 20 ° C. and a cooling air speed of 0.5 m / sec.
- Two-stage oiling was performed by the device 8 and the oiling device 9. As the spinning oil, 10% of the mixture of the polyether oil 15 and the low viscosity mineral oil 85 was adhered to the yarn (1.5% owf as a pure oil).
- the temperature of the first heating roll 11 (hereinafter referred to as 1FR) at 60 ° C. at a spinning speed of 700 m / min
- the temperature of the second heating roll 12 (hereinafter referred to as 1DR) was set to 110 ° C. and 1960 m /
- the first stage stretching (stretching ratio: 2.8 times) is performed in minutes
- the temperature of the third heating roll 13 (hereinafter referred to as 2DR) is set to 140 ° C. and the second stage stretching (at 3500 m / min).
- the film was wound at a speed of 3448 m / min (relaxation rate 1.5%).
- the multifilament comprised from the obtained polymer alloy fiber was 225 dtex and 15 filaments.
- the pressure on the back surface of the die under the following conditions was 2.4 MPa, and the average flow rate of the polymer in the die discharge hole was 0.16 m / sec.
- the cross section of the obtained fiber When a TEM observation of the cross section of the obtained fiber was performed, it had a uniformly dispersed sea island structure, and the island domain size was 0.03 to 0.2 ⁇ m in terms of diameter. Moreover, when the section of the yarn cross section was alkali etched to dissolve and remove polylactic acid, the island component was missing, and it was confirmed that polylactic acid formed the island component. Further, the area of the streaky crater on the fiber surface is about 3.8%, the strength of the obtained fiber is 3.1 cN / dtex, the elongation at break: 50%, the boiling water shrinkage ratio: 5.8%, the yarn spot U% : 1.0%, showing good fiber properties. Furthermore, the number of yarn cutting rotations by an abrasion test was 120, and good abrasion resistance was exhibited.
- Example 2 A multifilament was obtained in the same manner as in Example 1 except that the polylactic acid resin (A) and the polyolefin resin (B) were changed to 10 parts by weight and 90 parts by weight, respectively.
- the yarn forming property of Example 2 was extremely stable.
- the cross section of the obtained fiber was observed by TEM, it was found to have a uniformly dispersed sea-island structure, and the island domain size was 0.01 to 0.15 ⁇ m in terms of diameter, which is a more dispersed island component than in Example 1. The diameter was small.
- the section of the yarn cross section was alkali etched to dissolve and remove the polylactic acid, the island component was missing, and it was confirmed that the polylactic acid formed the island component.
- the obtained fiber had good fiber properties and abrasion resistance.
- Example 3 A multifilament was obtained in the same manner as in Example 1 except that the polylactic acid resin (A) and the polyolefin resin (B) were 40 parts by weight and 60 parts by weight, respectively.
- the yarn forming property of Example 3 was extremely stable.
- the cross section of the obtained fiber was observed with a TEM, it was found that the island structure was uniformly dispersed, and the island domain size was 0.03 to 0.6 ⁇ m in terms of diameter, and the island component was more dispersed than in Example 1.
- the diameter was large. Further, the area of the streaky crater after the alkali etching was about 5.5%, and although the wear resistance decreased due to the crater was observed, it had practical durability.
- Example 4 A multifilament was obtained in the same manner as in Example 1 except that the polylactic acid resin (A) and the polyolefin resin (B) were changed to 5 parts by weight and 95 parts by weight, respectively.
- the yarn forming property of Example 4 was extremely stable.
- the TEM observation of the cross section of the obtained fiber was performed, it had a uniformly dispersed sea island structure, and the island domain size was 0.01 to 0.1 ⁇ m in terms of diameter, and the dispersion diameter of the island component was extremely small. There were few islands. In addition, streak craters were not observed on the fiber surface of the multifilament.
- Example 5 A multifilament was obtained in the same manner as in Example 1 except that the polylactic acid-based resin (A) and the polyolefin-based resin (B) were changed to 47 parts by weight and 53 parts by weight, respectively.
- yarn breakage occurred 8 times when spinning a total of 200,000 m.
- the TEM observation of the cross section of the obtained fiber was performed, it had a non-uniform sea-island structure, and the island domain size had a very wide distribution diameter of 0.1 to 2.8 ⁇ m in terms of diameter. It was.
- the area of the streaky crater on the fiber surface was 17.3%, and a considerably large streaky crater was also observed as compared with Example 1.
- the yarn cutting rotation number by the abrasion test was 37, which was a practical level although the application was limited.
- Example 1 Spinning was carried out in the same manner as in Example 1 except that the compatibilizing agent (C) was not added. As a result, swelling occurred due to the ballast effect immediately below the die, and the elongation deformation on the spinning line was unstable, and the spinning speed. It was not possible to spin at 700 m / min.
- Comparative Example 2 The polylactic acid resin (A) and the polyolefin resin (B) are 70 parts by weight and 30 parts by weight, respectively, the temperature of the first heating roll is 80 ° C., and the spinning speed is 850 m / min (first stage draw ratio: 2.3). A multifilament was obtained in the same manner as in Example 1, except that it was taken up at a time. In Comparative Example 2, yarn breakage occurred 5 times when spinning a total of 200,000 m. When the TEM observation of the cross section of the obtained fiber was performed, it was a slightly non-uniform but dispersed sea island structure.
- the section of the yarn cross section was alkali etched to dissolve and remove the polylactic acid, the sea component was missing, and it was confirmed that polypropylene formed the island component.
- the abrasion resistance of the obtained fiber was a yarn cutting rotation number of 18, which was a level that could not be used in applications requiring abrasion resistance.
- Comparative Example 3 A multifilament was obtained in the same manner as in Comparative Example 2 except that only the polylactic acid resin (A) (polylactic acid P1) was used.
- the yarn forming property of Comparative Example 3 was stable as in Example 1.
- the obtained multifilament had an extremely low yarn cutting rotational speed of 8 in the abrasion test, and was a level that could not be used in applications that require abrasion resistance.
- Example 6 When spinning was carried out in the same manner as in Example 1 except that O2 was used as the polyolefin resin (B), swelling occurred due to the ballast effect directly under the base. In Example 6, yarn breakage occurred four times when spinning a total of 200,000 m.
- the island domain size was 0.05 to 0.6 ⁇ m in terms of diameter, which was larger than Example 1, and the yarn unevenness U% was slightly high at 2.1%. However, it had practical characteristics.
- Example 7 Spinning was carried out in the same manner as in Example 1 except that O3 was used as the polyolefin resin (B). As a result, swelling occurred due to the ballast effect immediately below the die, and the elongation deformation on the spinning line was unstable and thick. Has occurred. In Example 6, yarn breakage occurred 15 times when spinning a total of 200,000 m. When the TEM observation of the cross section of the obtained fiber was performed, the island domain size was 0.1 to 1.1 ⁇ m in terms of diameter, which was larger than Example 6, and the yarn spot U% was very high at 3.7%. Although the application was limited, it was at a practical level.
- Example 8 A multifilament was obtained in the same manner as in Example 1 except that polylactic acid P2 (melting point: 177 ° C., melt viscosity: 240 Pa ⁇ s) was used as the polylactic acid resin (A).
- the yarn-forming property of Example 7 was relatively stable, and the yarn breakage was 2 times when spinning a total of 200,000 m.
- the TEM observation of the cross section of the obtained fiber was performed, it was a sea island structure slightly inferior in uniformity, and the island domain size was 0.07 to 0.9 ⁇ m in terms of diameter.
- the abrasion resistance was 82 times of yarn cutting, and although it was inferior to Example 1, it was a level having practical durability.
- Example 9 Spinning was performed in the same manner as in Example 1 except that polylactic acid P2 was used as the polylactic acid resin (A) and O3 was used as the polyolefin resin (B). 20 times.
- the cross section of the obtained fiber was observed with a TEM, the island domain size was 0.1 to 2.2 ⁇ m in terms of diameter, which was larger than that of Example 7. Further, the wear resistance was 48 times of yarn cutting, and the utility was limited although the application was limited.
- Example 13 Spinning was carried out in the same manner as in Example 1 except that the compatibilizer (C) was changed to C2 and the addition amount was 10 parts by weight.
- the swelling just below the base was slightly large at the time of spinning, the spinning was relatively stable, and there were two breaks when spinning a total of 200,000 m.
- the cross section of the obtained fiber was observed with a TEM, the island domain size was 0.03 to 0.5 ⁇ m in terms of diameter, which was slightly larger than Example 1.
- the wear resistance was 88 times of yarn cutting, which was a level with no practical problem.
- Example 14 Spinning was performed in the same manner as in Example 13 except that the compatibilizer (C) was changed to C3.
- the swelling just below the base was greater than in Example 13, and the number of yarn breaks when spinning a total of 200,000 m was 9 times.
- the island domain size was 0.05 to 0.8 ⁇ m in terms of diameter, which was larger than Example 13.
- the abrasion resistance was 72 times of yarn cutting, and the use was limited, but it was at a practical level.
- Example 15 Spinning was performed in the same manner as in Example 1 except that a die having a diameter of 0.9 mm and a hole depth of 13.5 mm was used.
- the back pressure of the die during spinning of Example 15 was 5.2 MPa, and the average flow rate of the polymer in the die discharge hole was 0.16 m / sec.
- the swelling immediately below the base during spinning was large, and the yarn breakage reached 21 times when spinning a total of 200,000 m.
- the abrasion resistance was 76 times, and the use was limited, but it was at a practical level.
- Example 16 Spinning was carried out in the same manner as in Example 1 except that a die having a diameter of 0.7 mm and a hole depth of 1.4 mm was used.
- the back pressure of the die during spinning in Example 16 was 1.0 MPa, and the average flow rate of the polymer in the die discharge hole was 0.26 m / sec.
- the swollenness immediately below the base during spinning was larger than that in Example 1, but the spinning was relatively stable, and the number of yarn breaks when spinning a total of 200,000 m was three. Further, the wear resistance was 103 times when the yarn was cut, and it was at a level with no practical problem.
- Example 17 Spinning was performed in the same manner as in Example 1 except that a die having a diameter of 2.0 mm and a hole depth of 14 mm was used.
- the back pressure of the die during spinning in Example 17 was 1.0 MPa, and the average flow rate of the polymer in the die discharge hole was 0.03 m / sec.
- Example 17 although there was no swelling at the time of spinning, the yarn breakage at the time of spinning a total of 200,000 m was slightly lacking in stability at 5 times. Further, the wear resistance was 95 times that the yarn was cut, and there was no practical problem.
- Example 18 Six 225 decitex, 15 filament multifilaments obtained in Example 1 were drawn to 1350 decitex, 90 filaments, and a BCF yarn was obtained using a crimping apparatus equipped with an air stuffer device. At this time, the speed
- the film was wound at a winding tension of 120 g and a winding speed of 768 m / min.
- the obtained polymer alloy crimped yarn was 1380 dtex and 90 filaments, and the crimp elongation rate was 15.5%, showing good crimp characteristics. Further, when the carpet was made using the crimped yarn and evaluated, the wear loss rate was 18.8%, and the carpet exhibited good wear resistance. Moreover, the touch was good with moderate waist.
- the polymer alloy fiber of the present invention is used for clothing requiring wear resistance, such as outdoor wear, golf wear, athletic wear, ski wear, snowboard wear and sportswear such as pants thereof, casual wear such as blouson, coat, cold protection. Women and gentlemen's outerwear such as clothes and rainwear, as well as materials such as uniforms and various covers, and interior materials for automobiles that require durability and long-term durability and excellent aging characteristics In particular, it can be used for carpets for automobile interiors that require particularly high wear resistance and moisture aging characteristics.
- Spinning hopper 2 Twin screw extrusion kneader 3: Spinning block 4: Spinning pack 5: Spinneret 6: Circular chimney (yarn cooling device) 7: Yarn 8: Refueling device 1 9: Refueling device 2 10: Stretch roll 11: First heating roll (1FR) 12: Second heating roll (1DR) 13: Third heating roll (2DR) 14: Fourth roll (3DR) 15: Winder 16: Cooling air blowing surface
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Abstract
Description
本発明のポリマーアロイ繊維に用いるポリオレフィン系樹脂(B)は、相構造の制御のし易さより、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ4-メチル-1-ペンテン樹脂が好ましく、耐熱性の点から、ポリプロピレン樹脂がより好ましい。
捲縮伸長率(%)=[(L2-L1)/L1]×100。
試料(ポリ乳酸系樹脂)のクロロホルム溶液にテトラヒドロフランを混合し測定溶液とした。これをゲルパーミエーションクロマトグラフィー(GPC)で測定し、ポリスチレン換算で重量平均分子量を求めた。なお、繊維中のポリ乳酸の重量平均分子量を測定する場合には、試料をクロロホルムに溶かし、ポリオレフィン残渣を濾過して取り除き、該クロロホルム溶液を乾化してポリ乳酸系樹脂を取り出して測定を行った。
試料(ポリ乳酸系樹脂)1gをジクロロメタン20mlに溶解し、この溶液にアセトン5mlを添加した。さらにシクロヘキサンで定容して析出させ、島津社製GC17Aを用いて液体クロマトグラフにより分析し、絶対検量線にてラクチド量を求めた。なお、繊維中のポリ乳酸の場合は、予めポリ乳酸とポリオレフィンのブレンド比率を後述するTEM像から求め、上記ラクチド量をブレンド比率により補正して求めた。
精秤した試料(下記方法で抽出したポリ乳酸系樹脂)をo-クレゾール(水分5%)に溶解し、この溶液にジクロロメタンを適量添加した後、0.02規定のKOHメタノール溶液にて滴定することにより求めた。この時、乳酸の環状2量体であるラクチド等のオリゴマーが加水分解し、カルボキシル基末端を生じるため、ポリマーのカルボキシル基末端およびモノマー由来のカルボキシル基末端、オリゴマー由来のカルボキシル基末端の全てを合計したカルボキシル基末端濃度を求めた。なお、ポリマーアロイ繊維からポリ乳酸系樹脂を抽出する方法は特に限定されないが、本発明においてはクロロホルムを用いてポリ乳酸系樹脂を溶解、濾過してポリオレフィンを取り除き、濾過液を乾化させて抽出した。
パーキンエルマー社製示差走査型熱量計DSC-7型を用い、試料20mgを昇温速度10℃/分にて測定して得た融解吸熱曲線の極値を与える温度を融点(℃)とした。また、該極値を形成するピークとベースラインとで囲まれる面積(結晶融解ピーク面積)から、ポリマーの結晶融解熱量△H(J/g)を求めた。
東洋精機(株)社製キャピログラフ1Bを用い、チッソ雰囲気下において測定温度を230℃に設定し、剪断速度6.1(sec-1)でポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)及び相溶化剤(C)の溶融粘度の測定をした。測定は3回行い、平均値を溶融粘度とした。
ポリマーアロイ繊維の繊維軸と垂直の方向(繊維横断面方向)に超薄切片を切り出し、該切片を4万倍の透過型電子顕微鏡(TEM)にてブレンド状態を観察・撮影した。この撮影画像を三谷商事(株)の画像解析ソフト「WinROOF」を用い、島ドメイン(非染色部)のサイズとしてドメインを円と仮定し、ドメインの面積から換算される直径(直径換算)(2r)をドメインサイズとした。なお、計測するドメイン数は1試料あたり100個とし、ドメイン径の最も大きい10個および最も小さい10個の値を除いた80個のドメイン径について分布を求めた。
TEM装置:日立社製H-7100FA型、条件:加速電圧 100kV。
ポリマーアロイ繊維を水酸化ナトリウム20重量%溶液に一昼夜、浸漬(アルカリエッチング)した後、ニコンインステック(株)社製の電子顕微鏡ESEM-2700にて倍率5,000倍で繊維表面状態を観察、撮影した。この撮影画像を三谷商事(株)の画像解析ソフト「WinROOF」を用い、繊維表面中の任意の10μm×10μmの視野角で捉えられる筋状クレーターの面積を測定して求めた。なお、1試料あたり3カ所の視野について測定を行い、その平均値を筋状クレーターの面積比率(%)とした。
筋状クレーターの面積比率(%)=(筋状クレーター面積)/(繊維表面積)×100
検尺機にて100mの糸をかせ状に測長し、糸長100mの糸の重量を測定し、該重量を100倍することにより繊度(dtex)を求めた。測定は3回行い、その平均値を繊度(dtex)とした。
試料糸をオリエンテック(株)社製テンシロン(TENSILON)UCT-100でJIS L1013(化学繊維フィラメント糸試験方法、1998年)に示される定速伸長条件で測定した。掴み間隔(試料長)は200mmとした。なお、破断伸度はS-S曲線における最大強力を示した点の伸びから求めた。
試料糸を沸騰水に15分間浸積し、浸積前後の寸法変化から次式により求めた。
沸騰水収縮率(%)=[(L0-L1)/L0]×100
L0:試料をかせ取りし、初荷重0.088cN/dtex下で測定したかせ長。
L1:L0を測定したかせを無荷重の状態で沸騰水処理し風乾後、初荷重0.088
cN/dtex下で測定されるかせ長。
試料糸をZellweger uster社製UT4-CX/Mを用い、糸速度:200m/分、測定時間:1分間でU%(half Inert)を測定した。
環境温度25±5℃、相対湿度60±10%の雰囲気中に20時間以上放置されたパッケージ(捲縮糸巻取ドラムまたはボビン)から解舒した捲縮糸を、無荷重状態で30分間沸騰水で浸漬処理する。処理した後、前記環境下にて1昼夜(約24時間)風乾し、これを沸騰水処理後の捲縮糸の試料として使用する。この試料に1.8mg/dtexの初荷重をかけ、30秒経過した後に、試料長50cm(L1)にマーキングをする。次いで、初荷重の代わりに90mg/dtexの測定荷重をかけて30秒経過後に、試料長(L2)を測定する。そして下式により、沸騰水処理後の捲縮伸長率(%)を求める。
捲縮伸長率(%)=[(L2-L1)/L1]×100。
安藤鉄工所製のトワイン摩耗試験機を用い、P600番サンドペーパーをローラーに巻き付け、以下の条件にてローラーを回転させて糸切断までのローラー回転数を測定した。
回転体直径:40mm
糸の接触長:110mm
ローラー回転数:200rpm
測定荷重:0.4cN/dtex
島津製作所製SALD-2000Jを用い、レーザー回折法により結晶核剤の平均粒子径D50(μm)を測定した。また、得られた粒度分布から10μm以上の結晶核剤の体積%を求めた。
捲縮糸にS撚、Z撚をかけて2本合わせて撚糸した後、該撚糸を表糸としてPPスパンボンド不織布にタフティングした後、基布の裏にバッキング材を塗布して乾燥し、タフティングカーペットを得た(目付1200g/m2)。該タフティングカーペットを直径120mmの円形状に切り出し、中央に6mmの穴を空けて試験片とした。該試験片の重量W0を測定した後、ASTM D 1175(1994)に規定されるテーバー摩耗試験機(Rotary Abaster)に表面を上にして取り付け、H#18摩耗綸、圧縮荷重1kgf(9.8N)、試料ホルダ回転速度70rpm、摩耗回数5500回の摩耗試験を行い、摩耗試験後の試料重量W1を測定した。これらの測定値と下記の式を用いて摩耗減量率を算出した。
摩耗減量率(%)=(W0-W1)×100/(W2×A1/A0)
W0:測定前の円形カーペットの重量(g)
W1:測定後の円形カーペットの重量(g)
W2:カーペットの目付(g/m2)
A0:円形カーペットの全面積(m2)
A1:摩耗輪が接触する部分の全面積(m2)。
試料カーペットを手のひらで押したときの触感(柔軟性)および太陽光の下で目視して光沢感や光沢斑を確認し、触感、外観それぞれについて4段階評価した。
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光学純度99.8%のL乳酸から製造したラクチドを、ビス(2-エチルヘキサノエート)スズ触媒(ラクチド対触媒モル比=10000:1)存在させてチッソ雰囲気下180℃で240分間重合を行い、ポリ乳酸P1を得た。得られたポリ乳酸の重量平均分子量は23.3万であった。また、残留しているラクチド量は0.12重量%であった。
光学純度99.8%のL乳酸から製造したラクチドを、ビス(2-エチルヘキサノエート)スズ触媒(ラクチド対触媒モル比=10000:1)存在させてチッソ雰囲気下180℃で150分間重合を行い、ポリ乳酸P2を得た。得られたポリ乳酸の重量平均分子量は15万であった。また、残留しているラクチド量は0.10重量%であった。
(O1)プライムポリマー製“S119”(MFR:60[温度230℃]、融点166℃、結晶融解熱量110J/g、溶融粘度128Pa・s)
(O2)プライムポリマー製“ZS1337A”(MFR:26[温度230℃]、融点165℃、結晶融解熱量107J/g、溶融粘度195Pa・s)
(O3)プライムポリマー製“S115”(MFR:12[温度230℃]、融点165℃、結晶融解熱量102J/g、溶融粘度295Pa・s)
(C1)アミノ基変性SEBS(JSR製“ダイナロン”8630P、スチレン含有量15重量%、MFR15g/10分(230℃、21.2N))
(C2)イミン基変性SEBS(旭化成ケミカルズ製“タフテック”N503、スチレン含有量30重量%、MFR20g/10分(230℃、21.2N))
(C3)無水マレイン酸変性SEBS(クレイトン製“クレイトン”FG1924、スチレン含有量13重量%、無水マレイン酸含有量1重量%、MFR11g/10分(230℃、21.2N))
ポリ乳酸系樹脂(A)としてポリ乳酸P1(融点177℃、溶融粘度770Pa・s)、ポリオレフィン系樹脂(B)としてO1、相溶化剤としてC1(溶融粘度555Pa・s)をそれぞれ30重量部、70重量部、5重量部の割合(合計105重量部)でチップブレンドし、図3に示す2軸混練機(同方向2軸、軸径20mm、L/D45)を備えた紡糸装置のホッパー1に仕込んだ。なお、ポリ乳酸系樹脂(A)は110℃、真空下で約5時間乾燥し、水分率を80ppmに調湿した。2軸押出混練機2のジャケット温度を200℃、混練時の軸回転数を300rpmとして混練しながら溶融ポリマーを温度230℃に保温された紡糸ブロック3に導き、さらにギヤポンプにて計量・排出し、内蔵された紡糸パック4に溶融ポリマーを導き、紡糸口金5から紡出した。なお、紡糸パックの口金直上には絶対濾過径10μmのSUS不織布フィルター(不織布厚み:0.6mm)を組み込んだ。口金は直径0.9mm、孔深度6.3mmの丸孔を用いた。また、口金面温度は223℃であった。口金面下5cmの位置に吹出孔上端がくるように環状チムニー6(冷却長30cm)を設置して冷却風温度20℃、冷却風速度0.5m/秒で糸条7を冷却固化し、給油装置8および給油装置9により2段給油した。紡糸油剤にはポリエーテル系油剤15、低粘度鉱物油85の割合で混合したものを糸に対して10%付着させた(純油分として1.5%owf)。
ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)をそれぞれ10重量部、90重量部とした以外は、実施例1と同様にしてマルチフィラメントを得た。実施例2の製糸性は実施例1と同様、極めて安定していた。得られた繊維の横断面のTEM観察を行ったところ、均一に分散した海島構造をとっており、島ドメインサイズは直径換算で0.01~0.15μmと実施例1よりも島成分の分散径が小さかった。また、該糸断面の切片をアルカリエッチングしてポリ乳酸を溶解除去し観察したところ、島成分が欠落しており、ポリ乳酸が島成分を形成していることが確認された。また、得られた繊維は繊維物性、耐摩耗性共に良好であった。
ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)をそれぞれ40重量部、60重量部とした以外は、実施例1と同様にしてマルチフィラメントを得た。実施例3の製糸性は実施例1と同様、極めて安定していた。得られた繊維の横断面のTEM観察を行ったところ、均一に分散した海島構造をとっており、島ドメインサイズは直径換算で0.03~0.6μmと実施例1よりも島成分の分散径が大きかった。また、アルカリエッチング後の筋状クレーター面積も約5.5%であり、該クレーターに起因すると思われる耐摩耗性の低下が見られたが、実用耐久性を有するものであった。
ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)をそれぞれ5重量部、95重量部とした以外は、実施例1と同様にしてマルチフィラメントを得た。実施例4の製糸性は実施例1と同様、極めて安定していた。得られた繊維の横断面のTEM観察を行ったところ、均一に分散した海島構造をとっており、島ドメインサイズは直径換算で0.01~0.1μmと島成分の分散径が極めて小さく、島の数も少ないものであった。また、該マルチフィラメントの繊維表面には筋状クレーターが観察されなかった。
ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)をそれぞれ47重量部、53重量部とした以外は、実施例1と同様にしてマルチフィラメントを得た。実施例5は延べ20万m紡糸した際に糸切れが8回生じた。得られた繊維の横断面のTEM観察を行ったところ、不均一な海島構造をとっており、島ドメインサイズは直径換算で0.1~2.8μmと極めて広い分布の分散径を有していた。また、繊維表面の筋状クレーターの面積は17.3%であり、実施例1対比、かなり大きい筋状クレーターも観察された。また、摩耗試験による糸切断回転数が37回であり、用途は限定されるものの実用レベルであった。
相溶化剤(C)を添加しなかった以外は実施例1と同様にして紡糸を行ったところ、口金直下でのバラス効果により膨らみが生じ、さらに紡糸線上での伸長変形が不安定で紡糸速度700m/分で紡糸することができなかった。
ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)をそれぞれ70重量部、30重量部とし、第1加熱ロールの温度を80℃として紡糸速度850m/分(1段目延伸倍率:2.3倍)にて引き取った以外は、実施例1と同様にしてマルチフィラメントを得た。比較例2は延べ20万m紡糸した際に糸切れが5回発生した。得られた繊維の横断面のTEM観察を行ったところ、やや不均一ではあるが分散した海島構造をとっていた。また、該糸断面の切片をアルカリエッチングしてポリ乳酸を溶解除去し観察したところ、海成分が欠落しており、ポリプロピレンが島成分を形成していることが確認された。また、得られた繊維の耐摩耗性は糸切断回転数が18回であり、耐摩耗性が要求される用途では使用できないレベルであった。
ポリ乳酸系樹脂(A)(ポリ乳酸P1)のみとした以外は比較例2と同様にしてマルチフィラメントを得た。比較例3の製糸性は実施例1と同様、安定していた。得られたマルチフィラメントは摩耗試験による糸切断回転数が8回と極めて低く、耐摩耗性が要求される用途では使用できないレベルであった。
ポリオレフィン系樹脂(B)としてO2を用いた以外は、実施例1と同様にして紡糸を行ったところ、口金直下でのバラス効果により膨らみが生じていた。また、実施例6は延べ20万m紡糸した際に糸切れが4回生じた。得られた繊維の横断面のTEM観察を行ったところ、島ドメインサイズは直径換算で0.05~0.6μmと実施例1よりも大きく、糸斑U%も2.1%とやや高いものであったが、実用性のある特性を有していた。
ポリオレフィン系樹脂(B)としてO3を用いた以外は、実施例1と同様にして紡糸を行ったところ、口金直下でのバラス効果により膨らみが生じ、紡糸線上での伸長変形が不安定で太細が生じていた。また、実施例6は延べ20万m紡糸した際に糸切れが15回生じた。得られた繊維の横断面のTEM観察を行ったところ、島ドメインサイズは直径換算で0.1~1.1μmと実施例6よりも大きく、糸斑U%も3.7%と極めて高いものであったが、用途は限定されるものの実用レベルであった。
ポリ乳酸系樹脂(A)としてポリ乳酸P2(融点177℃、溶融粘度240Pa・s)、を用いた以外は実施例1と同様にしてマルチフィラメントを得た。実施例7の製糸性は比較的安定しており、延べ20万m紡糸した際の糸切れは2回であった。得られた繊維の横断面のTEM観察を行ったところ、やや均一性に劣る海島構造であり、島ドメインサイズは直径換算で0.07~0.9μmであった。また、耐摩耗性は糸切断回数82回であり、実施例1よりは劣るものの、実用耐久性を有するレベルであった。
ポリ乳酸系樹脂(A)としてポリ乳酸P2を、ポリオレフィン系樹脂(B)としてO3を用いた以外は実施例1と同様にして紡糸を行ったところ、延べ20万m紡糸した際の糸切れは20回であった。また、得られた繊維の横断面のTEM観察を行ったところ、島ドメインサイズは直径換算で0.1~2.2μmと実施例7よりも大きかった。また、耐摩耗性は糸切断回数48回であり、用途は限定されるものの、実用性を有するものであった。
相溶化剤(C1)のブレンド比率をそれぞれ0.5重量部、15重量部、30重量部とした以外は実施例1と同様にして紡糸を行った。相溶化剤を0.5重量部添加した実施例10は、紡糸時に口金直下での膨らみが大きく、紡糸線上での伸長変形が不安定で太細が生じており、その影響で糸斑U%も4.1%と極めて高いものであった。また、耐摩耗性は糸切断回数42回であり、用途は限定されるものの実用性を有するものであった。相溶化剤を15重量部とした実施例11は、実施例1よりは若干強度が低下するものの、その他の特性はほぼ実施例1と同等であり、高い実用性を有していた。相溶化剤を30重量%とした実施例12は繊維剛性が低下しており、実施例1よりもしなやかな特性を有していた。また、耐摩耗性は実施例1よりは劣るものの、十分な実用耐久性を有していた。
相溶化剤(C)をC2に変更し、添加量を10重量部にした以外は実施例1と同様にして紡糸を行った。実施例13は紡糸時に口金直下での膨らみがやや大きいものの、紡糸は比較的安定しており、延べ20万m紡糸した際の糸切れは2回であった。また、得られた繊維の横断面のTEM観察を行ったところ、島ドメインサイズは直径換算で0.03~0.5μmであり、実施例1よりはやや大きかった。また、耐摩耗性は糸切断回数88回であり、実用上問題のないレベルであった。
相溶化剤(C)をC3に変更した以外は実施例13と同様にして紡糸を行った。実施例14は実施例13よりもさらに口金直下での膨らみが大きく、延べ20万m紡糸した際の糸切れは9回であった。また、得られた繊維の横断面のTEM観察を行ったところ、島ドメインサイズは直径換算で0.05~0.8μmであり、実施例13よりさらに大きかった。また、耐摩耗性は糸切断回数72回であり、用途は限定されるものの、実用性のあるレベルであった。
口金として直径0.9mm、孔深度13.5mmのものを使用した以外は実施例1と同様にして紡糸を行った。実施例15の紡糸中の口金背面圧力は5.2MPa、口金吐出孔内のポリマーの平均流速は0.16m/秒であった。また、紡糸時に口金直下での膨らみが大きく、延べ20万m紡糸した際の糸切れは21回に及んだ。また、耐摩耗性は糸切断回数76回であり、用途は限定されるものの、実用性のあるレベルであった。
口金として直径0.7mm、孔深度1.4mmのものを使用した以外は実施例1と同様にして紡糸を行った。実施例16の紡糸中の口金背面圧力は1.0MPa、口金吐出孔内のポリマーの平均流速は0.26m/秒であった。実施例16は紡糸時に口金直下での膨らみが実施例1よりも大きいものの、紡糸は比較的安定しており、延べ20万m紡糸した際の糸切れは3回であった。また、耐摩耗性は糸切断回数103回であり、実用上問題のないレベルであった。
口金として直径2.0mm、孔深度14mmのものを使用した以外は実施例1と同様にして紡糸を行った。実施例17の紡糸中の口金背面圧力は1.0MPa、口金吐出孔内のポリマーの平均流速は0.03m/秒であった。実施例17は紡糸時の膨らみはないものの、延べ20万m紡糸した際の糸切れは5回とやや安定性に欠けた。また、耐摩耗性は糸切断回数95回であり、実用上問題のないレベルであった。
実施例1で得た225デシテックス、15フィラメントのマルチフィラメントを6本引き揃えて1350デシテックス、90フィラメントとし、エアスタッファ装置を備えた捲縮加工装置にてBCFヤーンを得た。このとき、第1供給ロール(非加熱)の速度を800m/分として第1加熱ロールに糸を送った。このときの第1加熱ロールは周速度808m/分(ストレッチ率1%)、表面温度145℃とした。第1加熱ロールにて熱処理後、連続してエアスタッファ装置にてノズル温度180℃で加熱圧空処理して捲縮加工を行い3次元捲縮を形成し、冷却ドラムに当てて引取った後、巻取張力120g、巻取速度768m/分で巻き取った。得られたポリマーアロイ捲縮糸は1380デシテックス、90フィラメントであり、捲縮伸長率が15.5%と良好な捲縮特性を示した。さらに該捲縮糸を用いてカーペットを作成して評価したところ、摩耗減量率は18.8%であり、カーペットとしても良好な耐摩耗性を示した。また、手触りは適度な腰があり良好なものであった。
2:2軸押出混練機
3:紡糸ブロック
4:紡糸パック
5:紡糸口金
6:環状チムニー(糸条冷却装置)
7:糸条
8:給油装置1
9:給油装置2
10:ストレッチロール
11:第1加熱ロール(1FR)
12:第2加熱ロール(1DR)
13:第3加熱ロール(2DR)
14:第4ロール(3DR)
15:巻取機
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Claims (11)
- ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)、および相溶化剤(C)とを配合してなるポリマーアロイからなるポリマーアロイ繊維であって、相溶化剤(C)が酸無水物基、カルボキシル基、アミノ基、イミノ基、アルコキシシリル基、シラノール基、シリルエーテル基、ヒドロキシル基およびエポキシ基から選択される少なくとも1種の官能基を含有するアクリル系エラストマーまたはスチレン系エラストマーであって、該ポリマーアロイのモルフォロジーが、ポリ乳酸系樹脂(A)が島成分を形成し、ポリオレフィン系樹脂(B)が海成分を形成した海島構造であることを特徴とするポリマーアロイ繊維。
- ポリマーアロイ繊維のアルカリエッチング後の繊維側面に存在する筋状クレーターの面積比率が10%以下であることを特徴とする請求項1記載のポリマーアロイ繊維。
ここで、
筋状クレーターの面積比率(%)=(筋状クレーター面積/繊維表面積)×100である。 - 島成分のドメインサイズが0.005~2μmであることを特徴とする請求項1または2記載のポリマーアロイ繊維。
- 温度230℃、ずり速度6.1(sec-1)での溶融粘度測定におけるポリ乳酸系樹脂(A)の溶融粘度ηAと、ポリオレフィン系樹脂(B)の溶融粘度ηBとの粘度比(ηA/ηB)が1.3~10であることを特徴とする請求項1~3のいずれか1項記載のポリマーアロイ繊維。
- ポリ乳酸系樹脂(A)と、ポリオレフィン系樹脂(B)の融点がいずれも150℃以上であることを特徴とする請求項1~4のいずれか1項記載のポリマーアロイ繊維。
- ポリマーアロイの組成が、ポリ乳酸系樹脂(A)とポリオレフィン系樹脂(B)の合計量を100重量部として、ポリ乳酸系樹脂(A)1~45重量部、ポリオレフィン系樹脂(B)99~55重量部、相溶化剤(C)1~30重量部であることを特徴とする請求項1~5のいずれか1項に記載のポリマーアロイ繊維。
- ポリマーアロイ繊維が以下の物性を満足するものである、請求項1~6のいずれか1項に記載のポリマーアロイ繊維。
強 度:1~7cN/dtex
沸収率:0~10% - 請求項1~7のいずれか1項記載のポリマーアロイ繊維から構成されるモノフィラメント又はマルチフィラメントであって、該フィラメントの糸斑U%(half Inert)が4%以下であることを特徴とするフィラメント。
- 請求項1~7のいずれか1項に記載のポリマーアロイ繊維および/又は請求項8に記載のフィラメントを少なくとも1部に含む繊維構造体。
- 繊維構造体が自動車内装用のカーペットである、請求項9に記載の繊維構造体。
- 温度230℃、ずり速度6.1(sec-1)での溶融粘度測定において、ポリ乳酸系樹脂(A)の溶融粘度ηAと、ポリオレフィン系樹脂(B)の溶融粘度ηBとの粘度比(ηA/ηB)が1.3~10であり、かつポリオレフィン系樹脂(B)の溶融粘度ηBが200Pa・s以下であって、さらに相溶化剤(C)として酸無水物基、カルボキシル基、アミノ基、イミノ基、アルコキシシリル基、シラノール基、シリルエーテル基、ヒドロキシル基およびエポキシ基から選択される少なくとも1種の官能基を含有するアクリル系エラストマーまたはスチレン系エラストマーを1~30重量部(ポリ乳酸系樹脂(A)とポリオレフィン系樹脂(B)の合計量を100重量部として算出)である条件で、ポリ乳酸系樹脂(A)、ポリオレフィン系樹脂(B)、相溶化剤(C)を溶融混練して一旦冷却した後チップ化するか、又は溶融状態のまま連続して紡糸装置に送り込み、計量した後、口金上に配置された金属不織布からなる多層フィルターを通し、更に口金面温度210~230℃における口金背面圧力が1~5MPa、口金吐出孔内のポリマーの平均流速が0.03~0.30m/秒となる口金にて吐出したモノフィラメント又はマルチフィラメントを、冷却、給油した後、300m/分以上で引き取り、一旦巻き上げるか、又は連続して延伸工程に導き、延伸温度60~140℃にて1段又は2段階で延伸して巻き取る事を特徴とするポリマーアロイ繊維の製造方法。
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KR101810274B1 (ko) | 2010-08-13 | 2017-12-18 | 킴벌리-클라크 월드와이드, 인크. | 개질된 폴리락트산 섬유 |
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