WO2017154665A1 - 可染性ポリオレフィン繊維およびそれからなる繊維構造体 - Google Patents
可染性ポリオレフィン繊維およびそれからなる繊維構造体 Download PDFInfo
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- WO2017154665A1 WO2017154665A1 PCT/JP2017/007733 JP2017007733W WO2017154665A1 WO 2017154665 A1 WO2017154665 A1 WO 2017154665A1 JP 2017007733 W JP2017007733 W JP 2017007733W WO 2017154665 A1 WO2017154665 A1 WO 2017154665A1
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- Prior art keywords
- fiber
- polyolefin fiber
- dyeable
- dyeable polyolefin
- polyolefin
- Prior art date
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- 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
- D01D5/36—Matrix structure; Spinnerette packs therefor
-
- 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
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
Definitions
- the present invention relates to a dyeable polyolefin fiber. More specifically, a bright and deep coloring property is imparted to polyolefin fibers with excellent lightness, and furthermore, oxidative degradation during tumbler drying and yellowing during long-term storage are suppressed, so that the fiber structure It is related with the dyeable polyolefin fiber which can be suitably employ
- Polyethylene fiber or polypropylene fiber which is a kind of polyolefin fiber, is excellent in lightness and chemical resistance, but has a drawback that it is difficult to dye because it does not have a polar functional group. Therefore, it is not suitable for apparel use.
- interior use such as tile carpets, household rugs, and car mats
- material uses such as ropes, curing nets, filter cloths, narrow tapes, braids and chairs. Are used in certain applications.
- Patent Document 1 attempts to improve the dyeability by modifying the surface of polyolefin fibers by graft copolymerization of vinyl compounds by ozone treatment or ultraviolet irradiation.
- Patent Document 2 proposes a dyeable polyolefin fiber obtained by blending polyester or polyamide into a polyolefin as a dyeable polymer.
- Patent Document 3 and Patent Document 4 attempt to improve color developability by making the dyeable polymer blended with polyolefin amorphous. Specifically, in Patent Document 3, a copolymerized polyester obtained by copolymerizing cyclohexanedimethanol, and in Patent Document 4, a copolymerized polyester obtained by copolymerizing isophthalic acid and cyclohexanedimethanol is blended into a polyolefin as a non-crystalline polymer that can be dyed. Dyeable polyolefin fibers have been proposed.
- JP-A-7-90783 JP-A-4-209824 Special table 2008-533315 JP-T-2001-522947
- Patent Document 1 requires a long time for ozone treatment and ultraviolet irradiation, so that the productivity is low and the barrier to industrialization is high.
- the object of the present invention is to solve the above-mentioned problems of the prior art, impart a bright and deep color development property to polyolefin fibers excellent in lightness, and further, oxidative degradation during tumbler drying and yellowing during long-term storage It is providing the dyeable polyolefin fiber which can be suitably employ
- An object of the present invention is a polymer alloy fiber having a sea-island structure in which a polyolefin (A) is a sea component and a copolymerized polyester (B) copolymerized with cyclohexanedicarboxylic acid is an island component,
- A polyolefin
- B copolymerized polyester
- cyclohexanedicarboxylic acid is an island component
- the compatibilizer (C) is selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an imino group. It is preferably at least one compound selected from a polyolefin resin, an acrylic resin, a styrene resin, and a conjugated diene resin, which contains at least one functional group, and is selected from an amino group and an imino group. More preferred is a styrene-ethylene-butylene-styrene copolymer containing at least one functional group.
- the dyeable polyolefin fiber is 3.0 to 20.0 parts by weight of the copolymer polyester (B) with respect to 100 parts by weight of the total of the polyolefin (A), the copolymer polyester (B), and the compatibilizer (C).
- the compatibilizer (C) is contained in an amount of 0.1 to 10.0 parts by weight.
- the dyeable polyolefin fiber has a maximum temperature of the sample during 100 hours of holding at a constant temperature of 150 ° C. in a test according to the oxidation heat generation test method (acceleration method) of polypropylene fiber by the Japan Chemical Fiber Association. It must be 155 ° C. or lower, the dyeing fastness to nitrogen oxides measured according to JIS L0855 is 4th grade or higher, and the phenolic yellowing measured according to ISO 105-X18 is 3rd grade or higher. preferable.
- the dyeable polyolefin fiber contains an antioxidant, the antioxidant is at least one selected from a phenolic compound, a phosphorus compound, and a hindered amine compound, and the hindered amine compound is an amino acid.
- An ether type hindered amine compound can be preferably employed.
- the present invention can be suitably used for a fiber structure characterized by using at least a part of the dyeable polyolefin fiber.
- a dyeable polyolefin fiber which is a polyolefin fiber excellent in lightness, has a vivid and deep color development property, and has suppressed oxidative degradation during tumbler drying and yellowing during long-term storage.
- the dyeable polyolefin fiber obtained by the present invention is made into a fiber structure, so that in addition to interior use and material use where conventional polyolefin-based fibers are used, clothing use and lightness and color developability are required. It can be suitably used in a wide range of applications.
- the dyeable polyolefin fiber of the present invention is a polymer alloy fiber having a sea-island structure in which a polyolefin (A) is a sea component and a copolymerized polyester (B) copolymerized with cyclohexanedicarboxylic acid is an island component.
- the dispersion diameter of the island component at 30 to 1000 nm.
- Coloring property can be imparted to the polyolefin (A) by arranging the copolymerized polyester (B) obtained by copolymerizing cyclohexanedicarboxylic acid in the polyolefin (A) on the island as a dyeable polymer.
- the dyeable polymer of the island component is exposed on the fiber surface. Therefore, it is possible to obtain a fiber having higher color developability, and further, the color development efficiency by the light transmitted to the island component is improved, and a vivid and deep color development can be realized.
- the polymer alloy fiber in the present invention is a fiber in which island components are discontinuously dispersed.
- the island component is discontinuous means that the island component has an appropriate length, and at any interval within the same single yarn, a cross-section perpendicular to the fiber axis, that is, a sea-island structure in the fiber cross-section Are in different states.
- the discontinuity of the island component in the present invention can be confirmed by the method described in the examples.
- the island components When the island components are discontinuously dispersed, the island components have a spindle shape, so that the coloring efficiency by light transmitted to the island components is improved, the sharpness is improved, and deep color development is obtained.
- the polymer alloy fiber according to the present invention is a core-sheath composite fiber in which one island is formed continuously and in the same shape in the fiber axis direction, or a sea island in which a plurality of islands are formed in the fiber axis direction and have the same shape.
- a polymer alloy fiber is, for example, from a polymer alloy composition formed by kneading a polyolefin (A) and a copolymerized polyester (B) copolymerized with cyclohexanedicarboxylic acid at an arbitrary stage before the completion of melt spinning. It can be obtained by molding.
- the sea component constituting the sea-island structure of the dyeable polyolefin fiber of the present invention is polyolefin (A). Since polyolefin has a low specific gravity, it is possible to obtain fibers having excellent lightness.
- the polyolefin (A) include, but are not limited to, polyethylene, polypropylene, polybutene-1, polymethylpentene and the like. Among them, polypropylene is preferable because of good molding processability and excellent mechanical properties, and polymethylpentene has a high melting point and excellent heat resistance, and has the lowest specific gravity among polyolefins and is excellent in lightness. preferable. Polypropylene can be particularly preferably used for clothing.
- the polyolefin (A) may be a homopolymer or a copolymer with another ⁇ -olefin.
- Other ⁇ -olefins hereinafter sometimes simply referred to as ⁇ -olefins may be copolymerized by one kind or two or more kinds.
- the carbon number of the ⁇ -olefin is preferably 2 to 20, and the molecular chain of the ⁇ -olefin may be linear or branched.
- Specific examples of the ⁇ -olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- Examples include, but are not limited to, eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 3-ethyl-1-hexene.
- the copolymerization rate of ⁇ -olefin is preferably 20 mol% or less.
- a copolymerization rate of ⁇ -olefin of 20 mol% or less is preferable because a dyeable polyolefin fiber having good mechanical properties and heat resistance can be obtained.
- the copolymerization ratio of ⁇ -olefin is more preferably 15 mol% or less, and further preferably 10 mol% or less.
- the island component constituting the sea-island structure of the dyeable polyolefin fiber of the present invention is a copolymerized polyester (B) obtained by copolymerizing cyclohexanedicarboxylic acid.
- Methods for improving the color development of the fiber include lowering the crystallinity of the polymer constituting the fiber and lowering the refractive index of the polymer, but lowering the refractive index of the polymer is more effective. Can be obtained.
- the refractive index of the polymer constituting the fiber when the refractive index of the polymer constituting the fiber is lowered, the reflected light from the fiber surface is reduced, the light penetrates sufficiently into the fiber, and a vivid and deep coloring property can be imparted. .
- the aromatic ring concentration of the polymer is a value calculated by the following formula using the copolymerization rate (mol%) of the copolymer component having an aromatic ring and the molecular weight (g / mol) of the repeating unit.
- Aromatic ring concentration (mol / kg) copolymerization ratio of copolymer component having aromatic ring (mol%) ⁇ 10 ⁇ molecular weight of repeating unit (g / mol).
- PET Polyethylene terephthalate
- terephthalic acid is a copolymer component having an aromatic ring.
- a copolymerized polyester obtained by copolymerizing cyclohexanedimethanol with PET has been proposed, and the copolymerization rate of the copolymer component having an aromatic ring is the same as that of PET, and the molecular weight of the repeating unit. Is higher than PET.
- the aromatic ring concentration calculated by the above formula is slightly lower than that of PET, and the refractive index is slightly lower than that of PET.
- the aromatic ring concentration calculated by the above formula is lower than that when cyclohexanedimethanol is copolymerized, and the refractive index is also lower, so that the color developability is higher, and vivid and deep color development is realized. be able to.
- the dispersion diameter of the island component in the fiber cross section of the dyeable polyolefin fiber of the present invention is 30 to 1000 nm.
- the dispersion diameter of the island component in a fiber cross section refers to the value measured by the method of an Example description.
- the dispersion diameter of the island component in the fiber cross section can be controlled to 30 to 1000 nm by the composite ratio of the polyolefin (A) and the copolymerized polyester (B), the addition of a compatibilizer (C) described later, and the like.
- the dispersion diameter of the island component in the cross section of the fiber is 30 nm or more, the dye is firmly taken into the copolymer polyester (B) of the island component, and the coloring efficiency by the light transmitted to the island component is improved. A certain color can be realized.
- the dispersion diameter of the island component in the fiber cross section is 1000 nm or less, the specific interface area of the sea-island interface can be sufficiently increased, so that the interface peeling and the wear caused by this can be suppressed. In addition to being excellent, the fastness to friction is good when dyed.
- the dispersion diameter of the island component is preferably 700 nm or less, more preferably 500 nm or less, and particularly preferably 300 nm or less.
- the copolymerized polyester (B) is copolymerized with 10 to 100 mol% of cyclohexanedicarboxylic acid with respect to the total dicarboxylic acid component of the copolymerized polyester (B).
- the copolyester (B) is defined as a polycondensate comprising at least three components selected from a dicarboxylic acid component and a diol component.
- a copolyester (B ) when all the dicarboxylic acid components consist only of cyclohexanedicarboxylic acid, that is, when cyclohexanedicarboxylic acid is 100 mol%, even if the diol component is one type or two or more types, a copolyester (B ).
- the copolymerization rate of cyclohexanedicarboxylic acid is 10 mol% or more, it is preferable because the refractive index of the polymer is low and vivid and deep color development can be realized.
- the copolymerization rate of cyclohexanedicarboxylic acid is more preferably 15 mol% or more, and further preferably 20 mol% or more.
- the copolymerization ratio of cyclohexanedicarboxylic acid is 30 mol% or more, the polymer becomes amorphous, and since more dye is exhausted to the polymer, higher color developability can be obtained. It can be suitably employed.
- the cyclohexanedicarboxylic acid may be any of 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, and may be used alone or in combination of two or more. May be used in combination.
- 1,4-cyclohexanedicarboxylic acid can be suitably employed from the viewpoints of heat resistance and mechanical properties.
- the copolymerized polyester (B) of the present invention may be copolymerized with other copolymerization components. Specific examples thereof include terephthalic acid, phthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, and 1,5-naphthalene.
- Aromatic dicarboxylic acids such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, anthracene dicarboxylic acid, malonic acid , Fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18- Octadecanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Aliphatic dicarboxylic acids such as carboxylic acids and dimer acids, aromatic diols such as catechol, naphthalenedio
- the dyeable polyolefin fiber of the present invention comprises the copolymer polyester (B) in an amount of 3.0 to 20.0 with respect to 100 parts by weight of the total of the polyolefin (A), the copolymer polyester (B), and the compatibilizer (C). It is preferable to contain by weight. If the content of the copolymerized polyester (B) is 3.0 parts by weight or more, the copolymerized polyester (B) having a low refractive index and high color developability is scattered in the polyolefin (A) having a low refractive index. Therefore, it is preferable because vivid and deep coloring can be realized.
- the content of the copolyester (B) is more preferably 3.5 parts by weight or more, and still more preferably 4.0 parts by weight or more.
- the content of the copolyester (B) is 20.0 parts by weight or less, coloring efficiency by light transmitted to the island component is improved by dyeing a large number of island components with respect to the sea component. It is preferable because vivid and deep color development can be obtained.
- the lightweight property of polyolefin (A) is not impaired, it is preferable.
- the content of the copolyester (B) is more preferably 17.0 parts by weight or less, and still more preferably 15.0 parts by weight or less.
- a compatibilizing agent (C) may be added.
- the compatibilizing agent (C) may be used for the purpose of improving yarn-manufacturability and obtaining high-quality fibers with small fineness spots and excellent uniformity in the fiber longitudinal direction.
- the compatibilizer (C) in the present invention depends on the copolymerization ratio of the cyclohexanedicarboxylic acid of the copolymer polyester (B), the composite ratio of the polyolefin (A) of the sea component and the copolymer polyester (B) of the island component, and the like. Can be selected as appropriate. In addition, only 1 type may be used for a compatibilizing agent (C), and 2 or more types may be used together.
- the compatibilizing agent (C) in the present invention has a hydrophobic component having a high affinity with the highly hydrophobic sea component polyolefin (A), and a functional group having a high affinity with the island component copolymer polyester (B). , Both being contained within a single molecule are preferred. Alternatively, both a hydrophobic component having a high hydrophobicity with the polyolefin (A) as a sea component and a functional group capable of reacting with the copolymer polyester (B) as an island component are both contained in a single molecule. Can be suitably used as the compatibilizing agent (C).
- hydrophobic component constituting the compatibilizer (C) examples include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene, and ethylene-propylene co-polymers.
- Polymer ethylene-butylene copolymer, propylene-butylene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, styrene-ethylene- Examples thereof include, but are not limited to, conjugated diene resins such as propylene-styrene copolymers.
- the functional group having a high affinity with the copolyester (B) or the functional group capable of reacting with the copolyester (B) constituting the compatibilizer (C) include an acid anhydride group, a carboxyl group, Examples include, but are not limited to, a hydroxyl group, an epoxy group, an amino group, and an imino group. Of these, amino groups and imino groups are preferred because of their high reactivity with the copolymerized polyester (B).
- compatibilizing agent (C) examples include maleic acid modified polyethylene, maleic anhydride modified polypropylene, maleic anhydride modified polymethylpentene, epoxy modified polypropylene, epoxy modified polystyrene, maleic anhydride modified styrene-ethylene-butylene-styrene copolymer.
- examples thereof include, but are not limited to, polymers, amine-modified styrene-ethylene-butylene-styrene copolymers, and imine-modified styrene-ethylene-butylene-styrene copolymers.
- the compatibilizer (C) in the present invention contains at least one functional group selected from an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an imino group, a polyolefin resin, an acrylic resin
- a styrene-ethylene-butylene-styrene copolymer containing at least one functional group selected from an amino group and an imino group has high reactivity with the copolymerized polyester (B), and is a polyolefin.
- the dyeable polyolefin fiber of the present invention is used as a compatibilizing agent with respect to a total of 100 parts by weight of the polyolefin (A), the copolyester (B), and the compatibilizing agent (C). It is preferable to contain 0.1 to 10.0 parts by weight of (C). If the content of the compatibilizing agent (C) is 0.1 parts by weight or more, since the compatibilizing effect of the polyolefin (A) and the copolyester (B) is obtained, the dispersion diameter of the island component becomes small, Aggregation of the dye compound can be suppressed to approach monodispersion, coloring efficiency is improved, and vivid and deep coloring is obtained, which is preferable.
- the content of the compatibilizer (C) is more preferably 0.3 parts by weight or more, and further preferably 0.5 parts by weight or more.
- the content of the compatibilizer (C) is 10.0 parts by weight or less, the fiber characteristics, appearance, and texture derived from the polyolefin (A) and the copolymerized polyester (B) constituting the dyeable polyolefin fiber. Can be maintained, which is preferable. Further, it is preferable because instability of the yarn maneuverability due to an excessive compatibilizing agent can be suppressed.
- the content of the compatibilizer (C) is more preferably 7.0 parts by weight or less, and still more preferably 5.0 parts by weight or less.
- the dyeable polyolefin fiber of the present invention preferably contains an antioxidant.
- Polyolefins are easily oxidatively decomposed by light and heat, so the inclusion of an antioxidant not only suppresses the oxidative degradation of polyolefins due to long-term storage and tumbler drying, but also improves the durability of fiber properties such as mechanical properties. It is preferable because it improves.
- the type, combination, and content of the antioxidant it may cause yellowing of the fiber due to nitrogen oxide gas or phenolic compound during long-term storage. It is preferable to select the kind, combination, and content of the antioxidant that can simultaneously suppress the change.
- phenolic yellowing refers to phenolic compound BHT (3,5-di-t-butyl-4-hydroxytoluene) (hereinafter simply referred to as “antioxidant”) contained in a packing material such as a plastic bag.
- BHT phenolic compound BHT
- antioxidant phenolic compound BHT
- BHT phenolic compound BHT
- pigments Since dyeing with a pigment is generally dark, the effect of yellowing of the fiber itself on the color tone after dyeing is small.
- the dyeable polyolefin fiber of the present invention can be dyed with a dye.
- Dye dyeing covers a wide range from light to dark, especially in the case of light colors, because the yellowing of the fiber itself has a large effect on the color tone after dyeing, so that the yellowing of the fiber caused by antioxidants is suppressed. Preferably it is.
- the antioxidant in the present invention is preferably any one of a phenol compound, a phosphorus compound, and a hindered amine compound. These antioxidants may use only 1 type and may use 2 or more types together.
- the phenolic compound in the present invention is a radical chain reaction inhibitor having a phenol structure, and only one type may be used or two or more types may be used in combination.
- pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (for example, Irganox 1010 manufactured by BASF)
- 2,4,6-tris (3 ′, 5′- Di-t-butyl-4′-hydroxybenzyl) mesitylene
- Adeka Stab AO-330 manufactured by ADEKA 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-t-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] -undecane (for example, Sumitomo Chemical's Smither GA-80, ADEKA Adeka Stub AO-80), 1,3,
- Cyanox 1790 has a high oxidative decomposition inhibiting effect, it can be suitably employed.
- 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10- Tetraoxaspiro [5,5] -undecane for example, Sumitomo Chemical Sumitizer GA-80, ADEKA Adeka Stub AO-80
- 1,3,5-tris [[4- (1,1-dimethylethyl) -3 -Hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (for example, THANOX 1790 manufactured by Tokyo Chemical Industry, Cyanox 1790 manufactured by CYTEC)
- THANOX 1790 manufactured by Tokyo Chemical Industry, Cyanox 1790 manufactured by CYTEC
- the phosphorus compound in the present invention is a phosphorus antioxidant that reduces peroxides without generating radicals and oxidizes itself, and may be used alone or in combination of two or more. May be.
- tris (2,4-di-t-butylphenyl) phosphite for example, Irgafos 168 manufactured by BASF
- 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2 4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane
- ADEKA ADEKA STAB PEP-36 can be suitably used because of its high oxidative degradation inhibiting effect.
- the hindered amine-based compound in the present invention is a hindered amine-based antioxidant that has an effect of capturing radicals generated by ultraviolet rays or heat and regenerating a phenol-based antioxidant deactivated by functioning as an antioxidant. May be used alone or two or more of them may be used in combination.
- an amino ether type hindered amine compound or a high molecular weight type hindered amine compound having a molecular weight of 1000 or more can be suitably employed.
- hindered amine compounds amino ether type hindered amine compounds have low basicity.
- the present inventors have found that the lower the basicity of the hindered amine compounds, the more the phenolic compounds and antioxidants that are antioxidants. It has been found that the phenolic compound contained is suppressed from changing to a quinone compound that causes yellowing. That is, an amino ether type hindered amine compound is preferable because yellowing of fibers caused by nitrogen oxide gas or phenolic compound during long-term storage can be suppressed.
- amino ether type hindered amine compounds include bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (for example, Adeka Stab LA-81 manufactured by ADEKA), bis (2) decanedioic acid bis [ 2,2,6,6-tetramethyl-1- (octyloxy) piperidin-4-yl] (for example, Tinuvin PA123 manufactured by BASF) and the like, but are not limited thereto.
- specific examples of hindered amine compounds with low basicity include 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexane.
- An ester of an acid for example, Tinuvin 249 manufactured by BASF
- the acid ester is not limited thereto.
- a high molecular weight hindered amine compound having a molecular weight of 1000 or more is preferable because it can suppress elution from the inside of the fiber by washing or cleaning using an organic solvent, and is excellent in durability against oxidative degradation.
- NN′—N ′′ —N ′ ′′-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine) (for example, SABOTAB UV119 from SABO), poly ((6-((1,1 , 3,3-tetramethylbutyl) amino) -1,3,5-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) imino) -1,6-hexane Diyl (2,2,6,6-tetramethyl-4-piperidinyl) imino)) (for example, CHIMASSORB 944 manufactured by BASF), dibutylamine-1,3,5-triazine
- the content of the antioxidant in the dyeable polyolefin fiber of the present invention is 0.1 to 5.0 with respect to 100 parts by weight of the total of the polyolefin (A), the copolyester (B), and the compatibilizer (C). It is preferable that it is a weight part. If the content of the antioxidant is 0.1 parts by weight or more, the effect of suppressing oxidative degradation can be imparted to the fiber, which is preferable. As for content of antioxidant, it is more preferable that it is 0.3 weight part or more, and it is still more preferable that it is 0.5 weight part or more.
- the content of the antioxidant is 5.0 parts by weight or less, the color tone of the fiber is not deteriorated and the mechanical properties are not impaired, which is preferable.
- the content of the antioxidant is more preferably 4.0 parts by weight or less, still more preferably 3.0 parts by weight or less, and particularly preferably 2.0 parts by weight or less.
- the dyeable polyolefin fiber of the present invention may have been subjected to various modifications by adding secondary additives.
- secondary additives include plasticizers, ultraviolet absorbers, infrared absorbers, fluorescent brighteners, mold release agents, antibacterial agents, nucleating agents, thermal stabilizers, antistatic agents, anti-coloring agents, and adjustments Examples include, but are not limited to, agents, matting agents, antifoaming agents, preservatives, gelling agents, latexes, fillers, inks, colorants, dyes, pigments, and fragrances. These secondary additives may be used alone or in combination of two or more.
- the fineness of the dyeable polyolefin fiber of the present invention as a multifilament is not particularly limited and may be appropriately selected depending on the application and required characteristics, but is preferably 10 to 3000 dtex.
- the fineness in the present invention refers to a value measured by the method described in the examples. If the fineness of the dyeable polyolefin fiber is 10 dtex or more, it is preferable because the yarn breakage is small and the process passability is good, the generation of fluff is small during use, and the durability is excellent.
- the fineness of the dyeable polyolefin fiber is more preferably 30 dtex or more, and further preferably 50 dtex or more.
- the fineness of the dyeable polyolefin fiber is 3000 dtex or less, the flexibility of the fiber and the fiber structure is not impaired, which is preferable.
- the fineness of the dyeable polyolefin fiber is more preferably 2500 dtex or less, and further preferably 2000 dtex or less.
- the single yarn fineness of the dyeable polyolefin fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required characteristics, but is preferably 0.5 to 20 dtex.
- the single yarn fineness in the present invention refers to a value obtained by dividing the fineness measured by the method described in the examples by the number of single yarns. If the single yarn fineness of the dyeable polyolefin fiber is 0.5 dtex or more, it is preferable because the yarn breakage is small, the process passability is good, the generation of fluff is small during use, and the durability is excellent.
- the single yarn fineness of the dyeable polyolefin fiber is more preferably 0.6 dtex or more, and further preferably 0.8 dtex or more.
- the single yarn fineness of the dyeable polyolefin fiber is 20 dtex or less, the flexibility of the fiber and the fiber structure is not impaired, which is preferable.
- the single yarn fineness of the dyeable polyolefin fiber is more preferably 15 dtex or less, and further preferably 12 dtex or less.
- the strength of the dyeable polyolefin fiber of the present invention is not particularly limited and can be appropriately selected according to the use and required characteristics, but is 1.0 to 6.0 cN / dtex from the viewpoint of mechanical characteristics. Is preferred.
- the strength in the present invention refers to a value measured by the method described in the examples. If the intensity
- the strength of the dyeable polyolefin fiber is more preferably 1.5 cN / dtex or more, and further preferably 2.0 cN / dtex or more. On the other hand, if the intensity
- the elongation of the dyeable polyolefin fiber of the present invention is not particularly limited and can be appropriately selected depending on the application and required characteristics, but is preferably 10 to 60% from the viewpoint of durability.
- the elongation in the present invention refers to a value measured by the method described in the examples. It is preferable that the elongation of the dyeable polyolefin fiber is 10% or more because the abrasion resistance of the fiber and the fiber structure is good, the generation of fluff is small during use, and the durability is good.
- the elongation of the dyeable polyolefin fiber is more preferably 15% or more, and further preferably 20% or more.
- the elongation of the dyeable polyolefin fiber is 60% or less, it is preferable because the dimensional stability of the fiber and the fiber structure becomes good.
- the elongation of the dyeable polyolefin fiber is more preferably 55% or less, and further preferably 50% or less.
- the fineness variation value U% (hi) of the dyeable polyolefin fiber of the present invention is preferably 0.1 to 1.5%.
- the fineness fluctuation value U% (hi) in the present invention refers to a value measured by the method described in the examples.
- the fineness variation value U% (hi) is an index of thickness variation in the fiber longitudinal direction, and the smaller the fineness variation value U% (hi), the smaller the thickness variation in the longitudinal direction of the fiber.
- the fineness fluctuation value U% (hi) is preferably as small as possible from the viewpoint of process passability and quality, but the lower limit is 0.1% as a manufacturable range.
- the fineness variation value U% (hi) of the dyeable polyolefin fiber is 1.5% or less, the uniformity in the longitudinal direction of the fiber is excellent, and fluff and thread breakage hardly occur. At this time, defects such as dyed spots and dyed streaks are unlikely to occur, and a high-quality fiber structure can be obtained, which is preferable.
- the fineness variation value U% (hi) of the dyeable polyolefin fiber is more preferably 1.2% or less, still more preferably 1.0% or less, and particularly preferably 0.9% or less. .
- the specific gravity of the dyeable polyolefin fiber of the present invention is preferably 0.83 to 1.0.
- the specific gravity in the present invention refers to a value measured by the method described in Examples, and is the true specific gravity.
- Polyolefin has a low specific gravity.
- the specific gravity of polymethylpentene is 0.83
- the specific gravity of polypropylene is 0.91.
- coloring property can be imparted to a polyolefin fiber having excellent lightness by using a polymer alloy fiber comprising a low specific gravity polyolefin and a dyeable copolymer polyester.
- the specific gravity of the dyeable polyolefin fiber varies depending on the specific gravity of the copolymer polyester (B) that is composited with the polyolefin (A), the composite ratio of the polyolefin (A) and the copolymer polyester (B), and the like.
- the specific gravity of the dyeable polyolefin fiber is preferably as small as possible from the viewpoint of lightness, and is preferably 1.0 or less.
- the specific gravity of the dyeable polyolefin fiber is 1.0 or less, it is preferable because both the lightness by the polyolefin (A) and the color development by the copolymerized polyester (B) can be achieved.
- the specific gravity of the dyeable polyolefin fiber is more preferably 0.97 or less, and further preferably 0.95 or less.
- the dyeable polyolefin fiber of the present invention has a maximum sample temperature of 155 in a test according to the oxidation heat generation test method (acceleration method) of polypropylene fiber by the Japan Chemical Fibers Association for 100 hours at a constant temperature of 150 ° C. It is preferable that it is below °C. If the maximum temperature of the dyeable polyolefin fiber that is a sample in the oxidation heat generation test is 155 ° C. or less, the oxidative degradation of the polyolefin during tumbler drying or long-term storage is suppressed, and fiber characteristics such as mechanical properties, texture, This is preferable because of excellent durability.
- the maximum temperature of the dyeable polyolefin fiber that is a sample in the oxidation heat generation test is more preferably 153 ° C. or less, and further preferably 151 ° C. or less.
- the dyeable polyolefin fiber of the present invention preferably has a dye fastness to nitrogen oxide (hereinafter sometimes simply referred to as nitrogen oxide fastness) measured in accordance with JIS L0855: 2005 of 4 or more. . If the dyeing fastness to the nitrogen oxide of the dyeable polyolefin fiber is 4th grade or more, the yellowing of the fiber due to the nitrogen oxide gas during long-term storage is suppressed. Even in the state, it is preferable because the quality of the fiber and the fiber structure is good. Moreover, since there are few dyeing spots accompanying the yellowing of a fiber and a fiber structure, it is preferable.
- the dyeing fastness to dyeing of the dyeable polyolefin fiber is more preferably 4-5 or higher, and further preferably 5th.
- the dyeable polyolefin fiber of the present invention preferably has a third or more phenolic yellowing measured according to ISO 105-X18: 2007.
- phenolic yellowing is yellowing of fibers caused by BHT of a phenolic compound contained as an antioxidant in a packing material such as a plastic bag. If the yellowishness of the dyeable polyolefin fiber is 3rd grade or higher, the yellowing of the fiber due to the phenolic compound of the packing agent during long-term storage is suppressed, and either state before dyeing or after dyeing Is preferable because the quality of the fiber and the fiber structure is good. Moreover, since there are few dyeing spots accompanying the yellowing of a fiber and a fiber structure, it is preferable. Phenolic yellowing of the dyeable polyolefin fiber is more preferably 3-4 or higher, more preferably 4 or higher, and particularly preferably 4 or 5 or higher.
- the dyeable polyolefin fiber of the present invention is not particularly limited with respect to the cross-sectional shape of the fiber, and can be appropriately selected according to the application and required characteristics, and may be a perfect circular cross section or a non-circular cross section. There may be. Specific examples of non-circular cross-sections include multilobal, polygonal, flat, elliptical, C-shaped, H-shaped, S-shaped, T-shaped, W-shaped, X-shaped, Y-shaped, paddy-shaped, cross-shaped, hollow However, it is not limited to these.
- the dyeable polyolefin fiber of the present invention is not particularly limited with respect to the fiber form, and may be any form such as a monofilament, a multifilament, and a staple.
- the dyeable polyolefin fiber of the present invention can be processed into false twists and twisted yarns in the same manner as general fibers, and weaving and knitting can be handled in the same manner as general fibers.
- the form of the fiber structure comprising the dyeable polyolefin fiber of the present invention is not particularly limited, and can be a woven fabric, a knitted fabric, a pile fabric, a nonwoven fabric, a spun yarn, a stuffed cotton or the like according to a known method.
- the fiber structure comprising the dyeable polyolefin fiber of the present invention may be any woven or knitted structure, such as plain weave, twill weave, satin weave, or these changed weaves, warp knitting, weft knitting, circular knitting. Further, a lace knitting or a change knitting thereof can be suitably employed.
- the dyeable polyolefin fiber of the present invention may be combined with other fibers by knitting or knitting when forming a fiber structure, or may be a fiber structure after blended yarn with other fibers. .
- a known melt spinning method or stretching method can be employed as a method for producing the dyeable polyolefin fiber of the present invention.
- the polyolefin (A), the copolyester (B), and the compatibilizer (C) before melt spinning, so that the water content is 0.3% by weight or less.
- a water content of 0.3% by weight or less is preferable because it does not cause foaming due to moisture during melt spinning and enables stable spinning. Further, it is preferable because deterioration of mechanical properties and deterioration of color tone due to hydrolysis are suppressed.
- the water content is more preferably 0.2% by weight or less, and further preferably 0.1% by weight or less.
- examples of methods for discharging from a spinneret into fiber yarns include the following examples, but are not limited thereto.
- a chip obtained by melting and kneading the sea component and island component in advance with an extruder or the like is dried as necessary, the chip is supplied to a melt spinning machine and melted. Weigh. Then, after introducing into the spinning pack heated in the spinning block and filtering the molten polymer in the spinning pack, there is a method of discharging from the spinneret into a fiber yarn.
- the chips are dried as necessary, and the sea component and the island component are mixed in the state of the chips, and then the mixed chips are supplied to the melt spinning machine to be melted and measured with a metering pump. Then, after introducing into the spinning pack heated in the spinning block and filtering the molten polymer in the spinning pack, there is a method of discharging from the spinneret into a fiber yarn.
- the fiber yarn discharged from the spinneret is cooled and solidified by a cooling device, taken up by a first godet roller, wound up by a winder through a second godet roller, and taken up as a wound yarn.
- a heating cylinder or a thermal insulation cylinder having a length of 2 to 20 cm may be provided below the spinneret as necessary.
- the spinning temperature in melt spinning can be appropriately selected according to the melting point and heat resistance of the polyolefin (A), the copolyester (B), and the compatibilizer (C), but it is 220 to 320 ° C. preferable. If the spinning temperature is 220 ° C. or higher, the elongation viscosity of the fiber yarn discharged from the spinneret is sufficiently lowered, so that the discharge is stable, and further, the spinning tension is not excessively increased and the yarn breakage is suppressed. This is preferable.
- the spinning temperature is more preferably 230 ° C. or higher, and further preferably 240 ° C. or higher. On the other hand, if the spinning temperature is 320 ° C.
- the spinning temperature is more preferably 300 ° C. or lower, and further preferably 280 ° C. or lower.
- the spinning speed in melt spinning can be appropriately selected according to the composite ratio of the polyolefin (A) and the copolyester (B), the spinning temperature, etc., but is preferably 500 to 6000 m / min.
- a spinning speed of 500 m / min or more is preferable because the running yarn is stable and yarn breakage can be suppressed.
- the spinning speed in the two-step method is more preferably 1000 m / min or more, and further preferably 1500 m / min or more.
- a spinning speed of 6000 m / min or less is preferable because stable spinning can be performed without yarn breakage by suppressing spinning tension.
- the spinning speed in the two-step method is more preferably 4500 m / min or less, and further preferably 4000 m / min or less.
- the spinning speed in the one-step method in which spinning and stretching are performed simultaneously without winding is preferably 500 to 5000 m / min for the low speed roller and 2500 to 6000 m / min for the high speed roller. It is preferable that the low-speed roller and the high-speed roller are within the above ranges because the running yarn is stabilized, yarn breakage can be suppressed, and stable spinning can be performed.
- the spinning speed in the one-step method is more preferably 1000 to 4500 m / min for the low speed roller, 3500 to 5500 m / min for the high speed roller, 1500 to 4000 m / min for the low speed roller, and 4000 to 5000 m / min for the high speed roller. More preferably.
- the heating method in stretching is not particularly limited as long as it is a device that can directly or indirectly heat the traveling yarn.
- Specific examples of the heating method include, but are not limited to, a heating roller, a hot pin, a hot plate, a liquid bath such as hot water and hot water, a gas bath such as hot air and steam, and a laser. These heating methods may be used alone or in combination. Heating methods include control of the heating temperature, uniform heating of the running yarn, and contact with the heating roller, contact with the hot pin, contact with the hot plate, and immersion in a liquid bath from the viewpoint of not complicating the device. It can be suitably employed.
- the stretching temperature can be appropriately selected according to the melting point of the polyolefin (A), the copolyester (B), the compatibilizer (C), the strength of the fiber after stretching, the elongation, and the like. However, it is preferably 50 to 150 ° C. If the drawing temperature is 50 ° C. or higher, the yarn supplied to the drawing is sufficiently preheated, the thermal deformation at the time of drawing becomes uniform, the occurrence of fineness unevenness can be suppressed, and the fiber longitudinal direction is uniform. It is preferable because a high-quality fiber having excellent properties can be obtained.
- the stretching temperature is more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher.
- the stretching temperature is 150 ° C. or lower, it is preferable because fusion and thermal decomposition of fibers due to contact with the heating roller can be suppressed, and process passability and quality are good. Moreover, since the slipperiness of the fiber with respect to a drawing roller becomes favorable, yarn breakage is suppressed and stable drawing can be performed, which is preferable.
- the stretching temperature is more preferably 145 ° C. or less, and further preferably 140 ° C. or less. Further, heat setting at 60 to 150 ° C. may be performed as necessary.
- the draw ratio in the case of stretching can be appropriately selected according to the elongation of the fiber before stretching, the strength and elongation of the fiber after stretching, etc., but is 1.02 to 7.0 times Is preferred.
- a draw ratio of 1.02 or more is preferable because mechanical properties such as fiber strength and elongation can be improved by drawing.
- the draw ratio is more preferably 1.2 times or more, and further preferably 1.5 times or more.
- the draw ratio is if the draw ratio is 7.0 times or less, yarn breakage during drawing is suppressed, and stable drawing can be performed.
- the draw ratio is more preferably 6.0 times or less, and still more preferably 5.0 times or less.
- the stretching speed in the case of stretching can be appropriately selected depending on whether the stretching method is a one-step method or a two-step method.
- the speed of the high-speed roller corresponding to the spinning speed corresponds to the stretching speed.
- the stretching speed is preferably 30 to 1000 m / min. A stretching speed of 30 m / min or more is preferable because the running yarn is stable and yarn breakage can be suppressed.
- the stretching speed is more preferably 50 m / min or more, and further preferably 100 m / min or more.
- a stretching speed of 1000 m / min or less is preferable because yarn breakage during stretching can be suppressed and stable stretching can be performed.
- the stretching speed when stretching by the two-step method is more preferably 900 m / min or less, and still more preferably 800 m / min or less.
- the dyeable polyolefin fiber of the present invention may be dyed in any state of a fiber or a fiber structure as necessary.
- a disperse dye can be suitably employed as the dye.
- the sea component polyolefin (A) constituting the dyeable polyolefin fiber is hardly dyed, the copolymer polyester (B) copolymerized with the island component cyclohexanedicarboxylic acid is dyed, so that it is vivid. It is possible to obtain a fiber and a fiber structure having a deep color developability.
- the dyeing method of the dyeable polyolefin fiber of the present invention is not particularly limited, and a cheese dyeing machine, a liquid dyeing machine, a drum dyeing machine, a beam dyeing machine, a jigger, a high-pressure jigger, etc. are suitably employed according to a known method. be able to.
- dye concentration and dyeing temperature there are no particular restrictions on the dye concentration and dyeing temperature, and a known method can be suitably employed. If necessary, scouring may be performed before the dyeing process, or reduction cleaning may be performed after the dyeing process.
- the dyeable polyolefin fiber of the present invention and the fiber structure comprising the same can impart vivid and deep color developability to the polyolefin fiber having excellent lightness. Therefore, in addition to applications where conventional polyolefin-based fibers are used, it is possible to expand to clothing applications and applications that require lightness and color development.
- Conventional polyolefin fibers are used in interiors such as tile carpets, household rugs, and automobile mats, bedding such as padding for futons, pillow filling materials, ropes, curing nets, filter cloths, and fine cloths. Examples include, but are not limited to, width tapes, braids, and chair materials.
- general clothing such as women's clothing, men's clothing, lining, underwear, down, vest, inner, outerwear, sports clothing such as windbreaker, outdoor wear, ski wear, golf wear, swimwear, etc.
- Futon side, futon cover, blanket, blanket side, blanket cover, pillowcase, bedclothes such as sheets, table cloth, curtains, interiors, belts, bags, sewing threads, sleeping bags, tents, etc.
- bedclothes such as sheets, table cloth, curtains, interiors, belts, bags, sewing threads, sleeping bags, tents, etc.
- DSC differential scanning calorimeter
- the melting peak temperature was calculated from the melting peak observed during the second temperature raising process. The measurement was performed 3 times per sample, and the average value was taken as the melting peak temperature. When a plurality of melting peaks were observed, the melting peak temperature was calculated from the melting peak on the lowest temperature side.
- Aromatic ring concentration For the polymer of the sea component (A) or island component (B), using the copolymerization rate (mol%) of the copolymer component having an aromatic ring and the molecular weight (g / mol) of the repeating unit, The aromatic ring concentration (mol / kg) was calculated.
- Aromatic ring concentration (mol / kg) copolymerization ratio of copolymer component having aromatic ring (mol%) ⁇ 10 ⁇ molecular weight of repeating unit (g / mol).
- Refractive index A press film was prepared using 1 g of a polymer of sea component (A) or island component (B), which had been vacuum-dried in advance, as a sample, using a 15 TON four-column single-acting ascending press manufactured by Gonno Hydraulic Co., Ltd.
- the sample and a spacer having a thickness of 50 ⁇ m were inserted into an infusible polyimide film (“Kapton” (registered trademark) 200H manufactured by Toray DuPont), inserted into a press machine, melted at 230 ° C. for 2 minutes, and then 2 MPa. Was pressed at a pressure of 1 mm for 1 minute, quickly removed from the press and rapidly cooled in water at 20 ° C.
- the polymer of the island component (B) of Comparative Example 1 has a melting temperature of 270 ° C., the polymer of the sea component (A) of Examples 25 to 29, and the island component (B of Examples 1, 2, 25, and Comparative Example 4). ) was changed to a melting temperature of 250 ° C. to produce a press film.
- Fineness (dtex) weight of fiber 100 m (g) ⁇ 100.
- F. Strength and elongation The strength and elongation were calculated according to JIS L1013: 2010 (chemical fiber filament yarn test method) 8.5.1 using the fiber obtained in the example as a sample. In an environment of a temperature of 20 ° C. and a humidity of 65% RH, a tensile test was performed using an orientec Tensilon UTM-III-100 model under the conditions of an initial sample length of 20 cm and a tensile speed of 20 cm / min.
- the strength (cN / dtex) is calculated by dividing the stress (cN) at the point indicating the maximum load by the fineness (dtex), and using the elongation (L1) and the initial sample length (L0) at the point indicating the maximum load, The elongation (%) was calculated by the formula. The measurement was carried out 10 times per sample, and the average values were taken as the strength and elongation.
- Elongation (%) ⁇ (L1-L0) / L0 ⁇ ⁇ 100.
- Fineness fluctuation value U% (hi) The fineness variation value U% (hi) is obtained by using the fiber obtained in the example as a sample and using a Worcester tester 4-CX manufactured by Zerbegger Worcester, measuring speed 200 m / min, measuring time 2.5 minutes, measured fiber length U% (half inert) was measured under conditions of 500 m and a twist number of 12000 / m (S twist). The measurement was performed five times for each sample, and the average value was defined as the fineness variation value U% (hi).
- the fiber cross section of the single yarn was observed using a plurality of single yarns manufactured under the same conditions as samples.
- the highest magnification at which the entire image of the single yarn could be observed was selected.
- the dispersion diameter of the island component existing in the fiber cross section of each single yarn was measured, and the average value of the dispersion diameters of a total of 100 island components was defined as the dispersion diameter of the island component.
- the specific gravity was calculated according to the floatation / sink method of JIS L1013: 2010 (chemical fiber filament yarn test method) 8.17 using the fiber obtained according to the example as a sample.
- a specific gravity measurement liquid was prepared using water as a heavy liquid and ethyl alcohol as a light liquid. In a constant temperature bath at a temperature of 20 ⁇ 0.1 ° C., about 0.1 g of the sample was allowed to stand in the specific gravity measurement liquid for 30 minutes, and then the sample was observed for its floating state.
- the sample After adding heavy liquid or light liquid according to the state of floatation, the sample was allowed to stand for 30 minutes, and after confirming that the sample was in the state of floatation and sedimentation, the specific gravity of the specific gravity measurement liquid was measured and the specific gravity of the sample was calculated. . In addition, the measurement was performed 5 times per sample and the average value was made into specific gravity.
- Tube dyeing after dyeing is carried out in an aqueous solution containing 2 g / L of sodium hydroxide, 2 g / L of sodium dithionite and 0.5 g / L of a surfactant GRANUP US-20 manufactured by Meisei Chemical Co., Ltd., with a bath ratio of 1: 100, After reducing and washing at 80 ° C. for 20 minutes, it was washed with running water for 30 minutes and dried in a hot air dryer at 60 ° C. for 60 minutes. After the reduction cleaning, the tubular knitting was dry-heat set at 135 ° C. for 1 minute, and finished.
- the L * value was measured by using a cylindrical knitting after finishing set as a sample and using a Minolta spectrocolorimeter CM-3700d model with a D65 light source, a viewing angle of 10 °, and an optical condition of SCE (regular reflected light removal method). In addition, the measurement was performed 3 times per sample, and the average value was defined as L * value.
- the light fastness was evaluated according to JIS L0843: 2006 (Test method for fastness to dyeing with respect to xenon arc lamp light) A method. Using the cylindrical knitting after finishing set produced in J above as a sample, Xenon arc lamp irradiation is performed using a Xenon weather meter X25 manufactured by Suga Test Instruments, and the degree of color fading of the sample is specified in JIS L0804: 2004. The light fastness was evaluated by classifying using a scale.
- the washing fastness was evaluated according to JIS L0844: 2011 (Testing method for fastness to dyeing for washing) A-2. Using the cylindrical knitting after finishing set made in J above as a sample, a sample with a white cloth (cotton 3-1 and nylon 7-1) specified in JIS L0803: 2011 using a round meter manufactured by Daiei Kagaku Seisakusho After the laundering treatment, the degree of color fastness of washing was evaluated by classifying the degree of color fading of the sample using the gray scale for color fading defined in JIS L0804: 2004.
- Friction fastness was evaluated according to the drying test of JIS L0849: 2013 (Test method for fastness to dyeing fastness to friction) 9.2 Friction tester type II (Gakushin type). Using the finished knitting tube knitting produced in J above as a sample, using a white cotton cloth (Cotton 3-1) as defined in JIS L0803: 2011 using a Gakushin friction tester RT-200 manufactured by Daiei Kagaku Seiki After the rubbing treatment, the degree of contamination of the white cotton fabric was evaluated using a gray scale for contamination specified in JIS L0805: 2005 to evaluate the friction fastness.
- the specific gravity of the fiber measured by said I was evaluated in four steps, S, A, B, and C, as a lightness index. Evaluation shows that S is the best, it gets worse in the order of A and B, and C is the worst.
- the specific gravity of the fiber is “less than 0.95” as S, “0.95 or more and less than 1.0” is A, “1.0 or more and less than 1.1” is B, and “1.1 or more” is C. A of 0.95 or more and less than 1.0 was regarded as acceptable.
- L * value measured in J above was used as an index of color developability, and was evaluated in four stages of S, A, B, and C. The smaller the value of L * value, the better the color developability. Evaluation shows that S is the best, it gets worse in the order of A and B, and C is the worst.
- L * The value is "less than 35" as S, "35 or more and less than 40" is A, "40 or more and less than 60" is B, "60 or more” is C, and "A or more” is "35 or more and less than 40". .
- the cylindrical container filled with the pre-treated cylindrical braid was placed in a constant temperature dryer set at 150 ° C., and the temperature of the thermocouple installed in the center of the cylindrical container (corresponding to the sample temperature) reached 150 ° C.
- a time change of 100 hours was recorded with a time of 0 minute, and the maximum temperature of the sample was measured. The measurement was performed twice for each sample, and the average value was taken as the maximum temperature of the sample in the oxidation heat generation test.
- the nitrogen oxide fastness was evaluated according to JIS L0855: 2005 (Testing method for fastness to dyeing with nitrogen oxide) weak test (1 cycle test). Using the scoured tubular knitting produced in J above as a sample, exposing to nitrogen oxides and post-processing with a buffered urea solution, the degree of color fading of the sample is specified in JIS L0804: 2004. Nitrogen oxide fastness was evaluated by using the grade.
- Phenolic yellowing was evaluated according to ISO 105-X18: 2007. Phenolic yellowing was evaluated by classifying the degree of discoloration of the sample using the gray scale defined in ISO 105-A03: 1993 using the scoured tubular knitting produced in J above as a sample.
- Example 1 95.2% by weight of polypropylene (PP) (Novatech MA2, manufactured by Nippon Polypro, melting peak temperature 159 ° C., MFR 16 g / 10 min), 4.8% by weight of polyethylene terephthalate copolymerized with 5 mol% of 1,4-cyclohexanedicarboxylic acid 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1 which is a phenolic compound as an antioxidant , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (CYANOX 1790 manufactured by CYTEC), 0.05 parts by weight of tris phosphite (2,4-di-t -Butylphenyl) (Irgafos 168 manufactured by BASF), 0.05 parts by weight, bis (1-undecanol) which is a hindered amine compound -2,2,6,
- a spun yarn was obtained by discharging from a discharge hole length of 0.23 mm, a hole number of 36, and a round hole.
- the spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 25 m / min, applied with an oil agent by an oil supply device, converged, and taken up by a first godet roller rotating at 3000 m / min.
- An undrawn yarn of 105 dtex-36f was obtained by winding with a winder through a second godet roller rotating at the same speed as the dead roller.
- the obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 90 ° C., a second hot roller temperature of 130 ° C. and a draw ratio of 2.1 times to obtain a drawn yarn of 50 dtex-36f.
- Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the resulting dyeable polyolefin fiber had a specific gravity of 0.93 and was excellent in lightness.
- the sea component made of polypropylene with a low refractive index cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate with a low refractive index and high color developability is finely dispersed as an island component, so a vivid and deep color is obtained.
- the color development and quality were acceptable.
- the light fastness, the fastness to washing, and the fastness to rubbing were all good, the entire fabric was dyed uniformly, and the leveling property was also good. From the results of the oxidation heat generation test, the oxidation heat generation was suppressed, and further, the fastness to nitrogen oxides and phenolic yellowing were good, and the yellowing of the fibers was also suppressed.
- Examples 2 to 7 A drawn yarn was produced in the same manner as in Example 1 except that the copolymerization rate of cyclohexanedicarboxylic acid was changed as shown in Table 1.
- Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the copolymerization rate of cyclohexanedicarboxylic acid increased, the refractive index decreased, the L * value also decreased, and the color developability improved.
- the copolymerization rate of cyclohexanedicarboxylic acid is 30 mol% or more, and the cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate becomes amorphous, so that the exhaustion rate of the dye is improved, and the brighter and deeper A certain color could be obtained, and the color development and quality were extremely excellent.
- Table 1 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- polyethylene terephthalate an island component
- polyethylene terephthalate has high crystallinity, so the exhaustion of the dye is insufficient, vivid and deep color development cannot be obtained, and color developability is insufficient. Yes, the quality was not acceptable.
- the fineness fluctuation value U% (hi) was high and the uniformity in the fiber longitudinal direction was insufficient, the leveling property was also inferior.
- Example 2 (Comparative Example 2, Examples 8-12, Comparative Example 3) A drawn yarn was produced in the same manner as in Example 3 except that the composite ratio of polypropylene and cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate was changed as shown in Table 2.
- Comparative Example 2 is a fiber made only of polypropylene. Since polypropylene does not have a polar functional group, it was hardly dyed with a dye and was extremely inferior in color developability. In Examples 8 to 12, the light weight, the color development, the leveling property, and the quality were acceptable levels for any composite ratio. In Comparative Example 3, since the composite ratio of cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate was high, the sea component was cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate and the island component was polypropylene, and the specific gravity was high and the lightness was poor. In addition, although the color developability is good, the island component polypropylene is hardly dyed, so that the level dyeability is poor, vivid and deep color development cannot be obtained, and the quality is inferior.
- Example 13 As a compatibilizing agent, maleic anhydride-modified polypropylene (POLYBOND 3200 manufactured by addvantt) was used in Example 13, maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer (Tuftec M1913 manufactured by Asahi Kasei Chemicals), and Example 15 Except that an amine-modified styrene-ethylene-butylene-styrene copolymer (Dynalon 8660P manufactured by JSR) was used and the composite ratio of polypropylene, cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate, and compatibilizer was as shown in Table 3, Example A drawn yarn was prepared in the same manner as in No. 3.
- Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the dispersion diameter of the island component is reduced due to the compatibilizing effect, and a vivid and deep color development can be obtained, and the color developability and the quality are extremely excellent. Further, due to the compatibilizing effect, the fineness variation value U% (hi) was low and the uniformity in the longitudinal direction of the fiber was good, so the leveling property was extremely excellent.
- Example 16 A drawn yarn was produced in the same manner as in Example 15 except that the composite ratio of polypropylene, cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate, and compatibilizer was changed as shown in Table 3.
- Table 3 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. In any composite ratio, the lightness, color development, leveling, and quality were acceptable levels.
- Example 23 The drawn yarn was the same as in Example 3, except that 1,4-cyclohexanedicarboxylic acid was changed to 1,2-cyclohexanedicarboxylic acid in Example 23 and 1,3-cyclohexanedicarboxylic acid in Example 24. Was made.
- Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the type of cyclohexanedicarboxylic acid was changed, the lightness, color development, leveling, and quality were acceptable levels.
- Examples 25 to 27 polypropylene was changed to polymethylpentene (PMP) (DX820, Mitsui Chemicals, melting peak temperature 232 ° C., MFR 180 g / 10 min), kneading temperature was changed to 260 ° C., and spinning temperature was changed to 260 ° C. Except for the above, drawn yarns were produced in the same manner as in Examples 2 to 4.
- PMP polymethylpentene
- Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when polymethylpentene was used as the polyolefin, vivid and deep color development could be obtained, and both color developability and quality were good. Moreover, the lightness and leveling property were acceptable levels.
- Examples 28 and 29 In Examples 13 and 15, except that polypropylene was changed to polymethylpentene (PMP) (Mitsui Chemicals DX820, melting peak temperature 232 ° C., MFR 180 g / 10 min), kneading temperature was changed to 260 ° C., and spinning temperature was changed to 260 ° C. A drawn yarn was produced in the same manner as in Examples 13 and 15.
- PMP polymethylpentene
- Table 4 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when polymethylpentene is used as the polyolefin, the dispersion diameter of the island component is reduced by virtue of the compatibilizing effect of the compatibilizing agent, and a vivid and deep color can be obtained. Met. Further, due to the compatibilizing effect, the fineness variation value U% (hi) was low and the uniformity in the longitudinal direction of the fiber was good, so the leveling property was extremely excellent.
- Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the refractive index decreased, the L * value also decreased, and the color developability improved.
- the refractive index tends to be higher than that of the cyclohexanedicarboxylic acid-copolymerized polyethylene terephthalate described in Examples 2 to 5 and 7, and vivid and deep color development cannot be obtained, and color development and quality are insufficient. . Further, in Comparative Examples 7 and 8, the leveling property was at an unacceptable level.
- Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Although leveling was good, vivid and deep color development was not obtained, and color development and quality were at a rejected level.
- Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Although leveling was good, vivid and deep color development was not obtained, and color development and quality were at a rejected level.
- sea component polypropylene and island component cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate are supplied to a pressure melter type composite spinning machine and melted separately to obtain a sea island type composite spinneret (discharge hole diameter 0.18 mm, discharge hole length 0. 23 mm, 32 islands, 36 holes, round holes) and drawn yarns were produced in the same manner as in Example 3 except that the composite ratio of the sea component and the island component was as shown in Table 5.
- Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the island component cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate is dyed, the sea component polypropylene covering the fiber surface layer is hardly dyed, so vivid and deep color development cannot be obtained. Both grades were rejected. Moreover, the whole fabric was not dyed uniformly and the leveling property was extremely inferior.
- Table 5 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers.
- the core component cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate is dyed, but the sheath component polypropylene covering the fiber surface layer is hardly dyed, so that a vivid and deep color development is obtained.
- the color development and quality were extremely poor.
- the whole fabric was not dyed uniformly and the leveling property was extremely inferior.
- the sheath component cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate covering the fiber surface layer is dyed, but the core component polypropylene is hardly dyed, so that a vivid and deep color development is obtained.
- the color development and quality were extremely poor.
- the whole fabric was not dyed uniformly, and leveling property was also a disqualified level.
- Example 30 In Example 15, except that the blending ratio of polypropylene, cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate and amine-modified styrene-ethylene-butylene-styrene copolymer was changed as shown in Table 6 and no antioxidant was added. A drawn yarn was produced in the same manner as in Example 15.
- Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Vivid and deep color development could be obtained, and the color development, leveling and quality were extremely excellent.
- Examples 31 to 40 A drawn yarn was produced in the same manner as in Example 30, except that the type and amount of the antioxidant were changed as shown in Table 6.
- the antioxidant in Example 34, 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl as a phenol compound was used.
- Example 35 pentaerythritol-tetrakis (3- (3,5-di- -T-butyl-4-hydroxyphenol) propionate) (Irganox 1010 from BASF),
- Examples 36 and 37 NN′—N ′′ —N ′ ′′-tetrakis (4,6-bis (4 Butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4 7-diazadecane-1,10-diamine) (SABOSTAB UV119 manufactured by SABO) and
- Examples 38 and 39 dibutylamine-1,3,5-triazine-N, N′-bis (2,2,6) is used as a hindered amine compound.
- Table 6 shows the evaluation results of the fiber characteristics and fabric characteristics of the obtained fibers. Even when the type, amount and combination of the antioxidants were changed, vivid and deep color development could be obtained, and the color development, leveling and quality were extremely excellent.
- the dyeable polyolefin fiber of the present invention has a bright and deep coloring property imparted to a lightweight polyolefin fiber, and further, oxidative degradation during tumbler drying and yellowing during long-term storage are suppressed. It can be used suitably as a fiber structure.
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Abstract
Description
海成分(A)または島成分(B)のポリマーを試料とし、TAインスツルメント製示差走査熱量計(DSC)Q2000型を用いて、融解ピーク温度を測定した。始めに、窒素雰囲気下で試料約5mgを0℃から280℃まで昇温速度50℃/分で昇温後、280℃で5分間保持して試料の熱履歴を取り除いた。その後、280℃から0℃まで急冷した後、再度0℃から280℃まで昇温速度3℃/分、温度変調振幅±1℃、温度変調周期60秒で昇温し、TMDSC測定を行った。JIS K7121:1987(プラスチックの転移温度測定方法)9.1に準じて、2回目の昇温過程中に観測された融解ピークより融解ピーク温度を算出した。測定は1試料につき3回行い、その平均値を融解ピーク温度とした。なお、融解ピークが複数観測された場合には、最も低温側の融解ピークから融解ピーク温度を算出した。
海成分(A)または島成分(B)のポリマーについて、芳香環を有する共重合成分の共重合率(mol%)および繰り返し単位の分子量(g/mol)を用いて、下記式によって芳香環濃度(mol/kg)を算出した。
事前に真空乾燥した海成分(A)または島成分(B)のポリマー1gを試料とし、ゴンノ油圧機製作所製15TON 4本柱単動上昇式プレス機を用いて、プレスフィルムを作製した。試料および厚さ50μmのスペーサーを不融性のポリイミドフィルム(東レ・デュポン製「カプトン」(登録商標)200H)に挟んだ状態でプレス機へ挿入し、230℃で2分間溶融させた後、2MPaの圧力で1分間プレスし、プレス機から速やかに取り出して20℃の水中で急冷して、厚さ50μmのプレスフィルムを得た。続いて、JIS K0062:1992(化学製品の屈折率測定方法)6.に記載のフィルム試料の測定方法に準じて、プレスフィルムの屈折率を測定した。温度20℃、湿度65%RHの環境下において、エルマ製アッベ屈折計ER-1型、中間液としてモノブロモナフタレン(nD=1.66)、ガラス片としてテストピース(nD=1.74)を用いて、1試料につき3回の測定を行い、その平均値を屈折率とした。
可染性ポリオレフィン繊維の原料として用いた海成分(A)、島成分(B)、相溶化剤(C)の合計を100重量部とし、複合比率として海成分(A)/島成分(B)/相溶化剤(C)[重量部]を算出した。
温度20℃、湿度65%RHの環境下において、INTEC製電動検尺機を用いて、実施例によって得られた繊維100mをかせ取りした。得られたかせの重量を測定し、下記式を用いて繊度(dtex)を算出した。なお、測定は1試料につき5回行い、その平均値を繊度とした。
強度および伸度は、実施例によって得られた繊維を試料とし、JIS L1013:2010(化学繊維フィラメント糸試験方法)8.5.1に準じて算出した。温度20℃、湿度65%RHの環境下において、オリエンテック社製テンシロンUTM-III-100型を用いて、初期試料長20cm、引張速度20cm/分の条件で引張試験を行った。最大荷重を示す点の応力(cN)を繊度(dtex)で除して強度(cN/dtex)を算出し、最大荷重を示す点の伸び(L1)と初期試料長(L0)を用いて下記式によって伸度(%)を算出した。なお、測定は1試料につき10回行い、その平均値を強度および伸度とした。
繊度変動値U%(hi)は、実施例によって得られた繊維を試料とし、ツェルベガーウースター製ウースターテスター4-CXを用いて、測定速度200m/分、測定時間2.5分、測定繊維長500m、撚り数12000/m(S撚り)の条件で、U%(half inert)を測定した。なお、測定は1試料につき5回行い、その平均値を繊度変動値U%(hi)とした。
実施例によって得られた繊維をエポキシ樹脂で包埋した後、LKB製ウルトラミクロトームLKB-2088を用いてエポキシ樹脂ごと、繊維軸に対して垂直方向に繊維を切断し、厚さ約100nmの超薄切片を得た。得られた超薄切片を固体の四酸化ルテニウムの気相中に常温で約4時間保持して染色した後、染色された面をウルトラミクロトームで切断し、四酸化ルテニウムで染色された超薄切片を作製した。染色された超薄切片について、日立製透過型電子顕微鏡(TEM)H-7100FA型を用いて、加速電圧100kVの条件で繊維軸に対して垂直な断面、すなわち繊維横断面を観察し、繊維横断面の顕微鏡写真を撮影した。観察は300倍、500倍、1000倍、3000倍、5000倍、10000倍、30000倍、50000倍の各倍率で行い、顕微鏡写真を撮影する際には100個以上の島成分が観察できる最も低い倍率を選択した。撮影された写真について、同一の写真から無作為に抽出した100個の島成分の直径を画像処理ソフト(三谷商事製WINROOF)で測定し、その平均値を島成分の分散径(nm)とした。繊維横断面に存在する島成分は必ずしも真円とは限らないため、真円ではない場合には外接円の直径を島成分の分散径として採用した。
比重は、実施例によって得られた繊維を試料とし、JIS L1013:2010(化学繊維フィラメント糸試験方法)8.17の浮沈法に準じて算出した。重液には水を用い、軽液にはエチルアルコールを用いて比重測定液を調製した。温度20±0.1℃の恒温槽中において、試料約0.1gを比重測定液に30分間放置した後、試料の浮沈状態を観察した。浮沈状態に応じて重液または軽液を添加して、さらに30分間放置した後に試料が浮沈平衡状態となったのを確認して、比重測定液の比重を測定し、試料の比重を算出した。なお、測定は1試料につき5回行い、その平均値を比重とした。
実施例によって得られた繊維を試料とし、英光産業製丸編機NCR-BL(釜径3インチ半(8.9cm)、27ゲージ)を用いて筒編み約2gを作製した後、炭酸ナトリウム1.5g/L、明成化学工業製界面活性剤グランアップUS-20 0.5g/Lを含む水溶液中、80℃で20分間精練後、流水で30分水洗し、60℃の熱風乾燥機内で60分間乾燥した。精練後の筒編みを135℃で1分間乾熱セットし、乾熱セット後の筒編みに対して、分散染料として日本化薬製Kayalon Polyester Blue UT-YAを1.3重量%加え、pHを5.0に調整した染色液中、浴比1:100、130℃で45分間染色後、流水で30分水洗し、60℃の熱風乾燥機内で60分間乾燥した。染色後の筒編みを、水酸化ナトリウム2g/L、亜ジチオン酸ナトリウム2g/L、明成化学工業製界面活性剤グランアップUS-20 0.5g/Lを含む水溶液中、浴比1:100、80℃で20分間還元洗浄後、流水で30分水洗し、60℃の熱風乾燥機内で60分間乾燥した。還元洗浄後の筒編みを135℃で1分間乾熱セットし、仕上げセットを行った。仕上げセット後の筒編みを試料とし、ミノルタ製分光測色計CM-3700d型を用いてD65光源、視野角度10°、光学条件をSCE(正反射光除去法)としてL*値を測定した。なお、測定は1試料につき3回行い、その平均値をL*値とした。
耐光堅牢度の評価は、JIS L0843:2006(キセノンアーク灯光に対する染色堅ろう度試験方法)A法に準じて行った。上記Jで作製した仕上げセット後の筒編みを試料として、スガ試験機製キセノンウェザーメーターX25を用いてキセノンアーク灯光照射を行い、試料の変退色の度合いをJIS L0804:2004に規定の変退色用グレースケールを用いて級判定することによって、耐光堅牢度を評価した。
洗濯堅牢度の評価は、JIS L0844:2011(洗濯に対する染色堅ろう度試験方法)A-2号に準じて行った。上記Jで作製した仕上げセット後の筒編みを試料として、大栄科学製作所製ラウンダメーターを用いて、JIS L0803:2011に規定の添付白布(綿3-1号、ナイロン7-1号)とともに試料を洗濯処理した後、試料の変退色の度合いをJIS L0804:2004に規定の変退色用グレースケールを用いて級判定することによって、洗濯堅牢度を評価した。
摩擦堅牢度の評価は、JIS L0849:2013(摩擦に対する染色堅ろう度試験方法)9.2摩擦試験機II形(学振形)法の乾燥試験に準じて行った。上記Jで作製した仕上げセット後の筒編みを試料として、大栄科学精機製学振型摩擦試験機RT-200を用いて、JIS L0803:2011に規定の白綿布(綿3-1号)で試料へ摩擦処理を施した後、白綿布の汚染の度合いをJIS L0805:2005に規定の汚染用グレースケールを用いて級判定することによって、摩擦堅牢度を評価した。
実施例によって得られた繊維について、上記Iで測定した繊維の比重を軽量性の指標として、S、A、B、Cの4段階で評価した。評価は、Sが最も良く、A、Bの順に悪くなり、Cが最も劣ることを示す。繊維の比重が「0.95未満」をS、「0.95以上1.0未満」をA、「1.0以上1.1未満」をB、「1.1以上」をCとし、「0.95以上1.0未満」のA以上を合格とした。
上記Jで測定したL*値を発色性の指標として、S、A、B、Cの4段階で評価した。L*値は数値が小さいほど、発色性に優れる。評価は、Sが最も良く、A、Bの順に悪くなり、Cが最も劣ることを示す。L*値が「35未満」をS、「35以上40未満」をA、「40以上60未満」をB、「60以上」をCとし、「35以上40未満」のA以上を合格とした。
上記Jで作製した仕上げセット後の筒編みについて、5年以上の品位判定の経験を有する検査員5名の合議によってS、A、B、Cの4段階で評価した。評価は、Sが最も良く、A、Bの順に悪くなり、Cが最も劣ることを示す。「非常に均一に染色されており、全く染め斑が認められない」をS、「ほぼ均一に染色されており、ほとんど染め斑が認められない」をA、「ほとんど均一に染色されておらず、うっすらと染め斑が認められる」をB、「均一に染色されておらず、はっきりと染め斑が認められる」をCとし、「ほぼ均一に染色されており、ほとんど染め斑が認められない」のA以上を合格とした。
上記Jで作製した仕上げセット後の筒編みについて、5年以上の品位判定の経験を有する検査員5名の合議によって、S、A、B、Cの4段階で評価した。評価は、Sが最も良く、A、Bの順に悪くなり、Cが最も劣ることを示す。「鮮やかで深みのある発色が十分であり、品位に極めて優れる」をS、「鮮やかで深みのある発色が概ね十分であり、品位に優れる」をA、「鮮やかで深みのある発色がほとんどなく、品位に劣る」をB、「鮮やかで深みのある発色がなく、品位に極めて劣る」をCとし、「鮮やかで深みのある発色が概ね十分であり、品位に優れる」のA以上を合格とした。
日本化学繊維協会によるポリプロピレン繊維の酸化発熱試験方法(加速法)に準じて行った。実施例によって得られた繊維を試料とし、英光産業製丸編機NCR-BL(釜径3インチ半(8.9cm)、27ゲージ)を用いて筒編みを作製し、洗濯およびタンブラー乾燥による前処理を行った。洗濯は、JIS L0217:1995(繊維製品の取扱いに関する表示記号及びその表示方法)103法に準じて行い、洗剤として花王製アタック、漂白剤として花王製ハイター(2.3ml/L)を加え、10回洗濯後に60℃のタンブラー乾燥機で30分間乾燥した。洗濯10回とタンブラー乾燥1回を1セットとし、計10セット繰り返して前処理を行った。
窒素酸化物堅牢度の評価は、JIS L0855:2005(窒素酸化物に対する染色堅ろう度試験方法)弱試験(1サイクル試験)に準じて行った。上記Jで作製した精練後の筒編みを試料として、窒素酸化物に暴露し、緩衝尿素溶液で後処理した後、試料の変退色の度合いをJIS L0804:2004に規定の変退色用グレースケールを用いて級判定することによって、窒素酸化物堅牢度を評価した。
フェノール性黄変の評価は、ISO 105-X18:2007に準じて行った。上記Jで作製した精練後の筒編みを試料として、試料の変退色の度合いをISO 105-A03:1993に規定のグレースケールを用いて級判定することによって、フェノール性黄変を評価した。
ポリプロピレン(PP)(日本ポリプロ製ノバテックMA2、融解ピーク温度159℃、MFR16g/10分)を95.2重量%、1,4-シクロヘキサンジカルボン酸を5mol%共重合したポリエチレンテレフタレートを4.8重量%の配合比とし、酸化防止剤として、フェノール系化合物である1,3,5-トリス[[4-(1,1-ジメチルエチル)-3-ヒドロキシ-2,6-ジメチルフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(CYTEC製CYANOX1790)を0.05重量部、リン系化合物である亜リン酸トリス(2,4-ジ-t-ブチルフェニル)(BASF製Irgafos168)を0.05重量部、ヒンダードアミン系化合物であるビス(1-ウンデカノキシ-2,2,6,6-テトラメチルピペリジン-4-イル)カーボネート(ADEKA製アデカスタブLA-81)を0.5重量部添加して、二軸エクストルーダーを用いて混練温度230℃で混練を行った。二軸エクストルーダーより吐出されたストランドを水冷した後、ペレタイザーにて5mm長程度にカットして、ペレットを得た。得られたペレットを95℃で12時間真空乾燥した後、エクストルーダー型溶融紡糸機へ供給して溶融させ、紡糸温度250℃、吐出量31.5g/分で紡糸口金(吐出孔径0.18mm、吐出孔長0.23mm、孔数36、丸孔)から吐出させて紡出糸条を得た。この紡出糸条を風温20℃、風速25m/分の冷却風で冷却し、給油装置で油剤を付与して収束させ、3000m/分で回転する第1ゴデットローラーで引き取り、第1ゴデットローラーと同じ速度で回転する第2ゴデットローラーを介して、ワインダーで巻き取って105dtex-36fの未延伸糸を得た。得られた未延伸糸を第1ホットローラー温度90℃、第2ホットローラー温度130℃、延伸倍率2.1倍の条件で延伸し、50dtex-36fの延伸糸を得た。
シクロヘキサンジカルボン酸の共重合率を表1に示すとおり変更した以外は、実施例1と同様に延伸糸を作製した。
ポリプロピレン(PP)を95.2重量%、ポリエチレンテレフタレート(PET)(東レ製T701T、融解ピーク温度257℃)を4.8重量%の複合比率とし、混練温度を280℃、紡糸温度を285℃に変更した以外は、実施例1と同様に延伸糸を作製した。
ポリプロピレン、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレートの複合比率を表2に示すとおり変更した以外は、実施例3と同様に延伸糸を作製した。
相溶化剤として、実施例13では無水マレイン酸変性ポリプロピレン(addivant製POLYBOND3200)、実施例14では無水マレイン酸変性スチレン-エチレン-ブチレン-スチレン共重合体(旭化成ケミカルズ製タフテックM1913)、実施例15ではアミン変性スチレン-エチレン-ブチレン-スチレン共重合体(JSR製ダイナロン8660P)を用い、ポリプロピレン、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレート、相溶化剤の複合比率を表3に示すとおりとした以外は、実施例3と同様に延伸糸を作製した。
ポリプロピレン、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレート、相溶化剤の複合比率を表3に示すとおり変更した以外は、実施例15と同様に延伸糸を作製した。
実施例3において1,4-シクロヘキサンジカルボン酸を、実施例23では1,2-シクロヘキサンジカルボン酸、実施例24では1,3-シクロヘキサンジカルボン酸に変更した以外は、実施例3と同様に延伸糸を作製した。
実施例2~4において、ポリプロピレンをポリメチルペンテン(PMP)(三井化学製DX820、融解ピーク温度232℃、MFR180g/10分)に変更し、混練温度を260℃、紡糸温度を260℃に変更した以外は、実施例2~4と同様に延伸糸を作製した。
実施例13、15においてポリプロピレンをポリメチルペンテン(PMP)(三井化学製DX820、融解ピーク温度232℃、MFR180g/10分)、混練温度を260℃、紡糸温度を260℃に変更した以外は、実施例13、15と同様に延伸糸を作製した。
実施例2~5、7において、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレートを、シクロヘキサンジメタノール共重合ポリエチレンテレフタレートに変更した以外は、実施例2~5、7と同様に延伸糸を作製した。
特表2008-533315号公報に記載の実施例1を参考に、ポリプロピレン、シクロヘキサンジメタノールを31mol%共重合したポリエチレンテレフタレート、無水マレイン酸変性ポリプロピレン(addivant製POLYBOND3200)を95.0/4.8/0.2の複合比率とした以外は、実施例1と同様に延伸糸を作製した。
特表2001-522947号公報に記載の実施例1を参考に、シクロヘキサンジメタノールを31mol%共重合したポリエチレンテレフタレートを、イソフタル酸を20mol%およびシクロヘキサンジメタノールを20mol%共重合したポリエチレンテレフタレートに変更した以外は、比較例9と同様に延伸糸を作製した。
ポリプロピレン(PP)(日本ポリプロ製ノバテックMA2、融解ピーク温度159℃、MFR16g/10分)へ酸化防止剤として、フェノール系化合物である1,3,5-トリス[[4-(1,1-ジメチルエチル)-3-ヒドロキシ-2,6-ジメチルフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(CYTEC製CYANOX1790)を0.05重量部、リン系化合物である亜リン酸トリス(2,4-ジ-t-ブチルフェニル)(BASF製Irgafos168)を0.05重量部、ヒンダードアミン系化合物であるビス(1-ウンデカノキシ-2,2,6,6-テトラメチルピペリジン-4-イル)カーボネート(ADEKA製アデカスタブLA-81)を0.5重量部添加して、二軸エクストルーダーを用いて混練温度230℃で混練を行った。二軸エクストルーダーより吐出されたストランドを水冷した後、ペレタイザーにて5mm長程度にカットして、海成分に用いるポリプロピレンのペレットを得た。海成分のポリプロピレンと、島成分のシクロヘキサンジカルボン酸共重合ポリエチレンテレフタレートをプレッシャーメルター型複合紡糸機へ供給して別々に溶融させ、海島型複合用紡糸口金(吐出孔径0.18mm、吐出孔長0.23mm、島数32、孔数36、丸孔)から吐出させ、海成分と島成分の複合比率を表5に示すとおりとした以外は、実施例3と同様に延伸糸を作製した。
ポリプロピレンとして比較例11で作製したポリプロピレンのペレットを用い、ポリプロピレンと、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレートをプレッシャーメルター型複合紡糸機へ供給して別々に溶融させ、芯鞘型複合用紡糸口金(吐出孔径0.18mm、吐出孔長0.23mm、孔数36、丸孔)から吐出させ、芯成分と鞘成分の複合比率を表5に示すとおりとした以外は、実施例3と同様に延伸糸を作製した。なお、比較例12、13においては、海成分は鞘成分に相当し、島成分は芯成分に相当する。
実施例15において、ポリプロピレン、シクロヘキサンジカルボン酸共重合ポリエチレンテレフタレート、アミン変性スチレン-エチレン-ブチレン-スチレン共重合体の配合比を表6に示すとおり変更し、酸化防止剤を添加しないこと以外は、実施例15と同様に延伸糸を作製した。
酸化防止剤の種類、量を表6に示すとおり変更した以外は、実施例30と同様に延伸糸を作製した。酸化防止剤について、実施例34ではフェノール系化合物として3,9-ビス[1,1-ジメチル-2-[β-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]エチル]-2,4,8,10-テトラオキサスピロ[5,5]-ウンデカン(ADEKA製アデカスタブAO-80)、実施例35ではフェノール系化合物としてペンタエリスリトール-テトラキス(3-(3,5-ジ-t-ブチル-4-ヒドロキシフェノール)プロピオネート)(BASF製Irganox1010)、実施例36、37ではヒンダードアミン系化合物としてN-N’-N’’-N’’’-テトラキス(4,6-ビス(ブチル-(N-メチル-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ)トリアジン-2-イル)-4,7-ジアザデカン-1,10-ジアミン)(SABO製SABOSTAB UV119)、実施例38、39ではヒンダードアミン系化合物としてジブチルアミン-1,3,5-トリアジン-N,N’-ビス(2,2,6,6-テトラメチル-4-ピペリジル)-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物(BASF製CHIMASSORB2020)、実施例40ではリン系化合物として3,9-ビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ[5,5]ウンデカン(ADEKA製アデカスタブPEP-36)を添加した。
Claims (14)
- ポリオレフィン(A)が海成分、シクロヘキサンジカルボン酸を共重合した共重合ポリエステル(B)が島成分である海島構造からなるポリマーアロイ繊維であって、繊維横断面における島成分の分散径が30~1000nmであることを特徴とする可染性ポリオレフィン繊維。
- 共重合ポリエステル(B)が、全ジカルボン酸成分に対し、シクロヘキサンジカルボン酸を10~100mol%共重合していることを特徴とする請求項1記載の可染性ポリオレフィン繊維。
- 相溶化剤(C)を含有することを特徴とする請求項1または2記載の可染性ポリオレフィン繊維。
- 相溶化剤(C)が、酸無水物基、カルボキシル基、ヒドロキシル基、エポキシ基、アミノ基およびイミノ基から選択される少なくとも1種の官能基を含有する、ポリオレフィン系樹脂、アクリル系樹脂、スチレン系樹脂および共役ジエン系樹脂から選択される1種以上の化合物であることを特徴とする請求項3記載の可染性ポリオレフィン繊維。
- 相溶化剤(C)が、アミノ基およびイミノ基から選択される少なくとも1種の官能基を含有する、スチレン-エチレン-ブチレン-スチレン共重合体であることを特徴とする請求項3または4記載の可染性ポリオレフィン繊維。
- ポリオレフィン(A)、共重合ポリエステル(B)、相溶化剤(C)の合計100重量部に対し、共重合ポリエステル(B)を3.0~20.0重量部含有することを特徴とする請求項3~5のいずれか一項に記載の可染性ポリオレフィン繊維。
- ポリオレフィン(A)、共重合ポリエステル(B)、相溶化剤(C)の合計100重量部に対し、相溶化剤(C)を0.1~10.0重量部含有することを特徴とする請求項3~6のいずれか一項記載の可染性ポリオレフィン繊維。
- 日本化学繊維協会によるポリプロピレン繊維の酸化発熱試験方法(加速法)に準じた試験において、150℃の恒温状態で100時間保持する間の試料の最高温度が155℃以下であることを特徴とする請求項1~7のいずれか一項記載の可染性ポリオレフィン繊維。
- JIS L0855に準じて測定した窒素酸化物に対する染色堅ろう度が4級以上であることを特徴とする請求項1~8のいずれか一項記載の可染性ポリオレフィン繊維。
- ISO 105-X18に準じて測定したフェノール性黄変が3級以上であることを特徴とする請求項1~9のいずれか一項記載の可染性ポリオレフィン繊維。
- 酸化防止剤を含有することを特徴とする請求項1~10のいずれか一項記載の可染性ポリオレフィン繊維。
- 前記酸化防止剤が、フェノール系化合物、リン系化合物、ヒンダードアミン系化合物から選ばれる少なくとも一種であることを特徴とする請求項11記載の可染性ポリオレフィン繊維。
- 前記ヒンダードアミン系化合物が、アミノエーテル型ヒンダードアミン系化合物であることを特徴とする請求項12記載の可染性ポリオレフィン繊維。
- 請求項1~13のいずれか一項記載の可染性ポリオレフィン繊維を少なくとも一部に用いることを特徴とする繊維構造体。
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WO2018034160A1 (ja) * | 2016-08-18 | 2018-02-22 | 東レ株式会社 | 可染性ポリオレフィン繊維からなる仮撚加工糸 |
WO2018079152A1 (ja) * | 2016-10-25 | 2018-05-03 | 東レ株式会社 | ポリマーアロイ繊維およびそれからなる繊維構造体 |
WO2019142718A1 (ja) * | 2018-01-18 | 2019-07-25 | 東レ株式会社 | 可染性ポリオレフィン繊維およびそれからなる繊維構造体 |
JP2019127679A (ja) * | 2018-01-22 | 2019-08-01 | 東レ株式会社 | 可染性ポリオレフィン芯鞘型複合繊維およびそれからなる繊維構造体 |
CN110295411A (zh) * | 2018-03-23 | 2019-10-01 | 东丽纤维研究所(中国)有限公司 | 一种可染聚烯烃海岛复合纤维 |
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WO2023112850A1 (ja) * | 2021-12-17 | 2023-06-22 | 東レ株式会社 | ポリプロピレン短繊維 |
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JPWO2019142718A1 (ja) * | 2018-01-18 | 2020-11-19 | 東レ株式会社 | 可染性ポリオレフィン繊維およびそれからなる繊維構造体 |
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EP3741885A4 (en) * | 2018-01-18 | 2021-10-20 | Toray Industries, Inc. | COLORABLE POLYOLEFIN FIBERS AND FIBER STRUCTURES THEREFORE |
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TWI814764B (zh) * | 2018-01-18 | 2023-09-11 | 日商東麗股份有限公司 | 可染性聚烯烴纖維及包含其之纖維構造體 |
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JP7290025B2 (ja) | 2018-01-22 | 2023-06-13 | 東レ株式会社 | 可染性ポリオレフィン芯鞘型複合繊維およびそれからなる繊維構造体 |
CN110295411A (zh) * | 2018-03-23 | 2019-10-01 | 东丽纤维研究所(中国)有限公司 | 一种可染聚烯烃海岛复合纤维 |
JP2020020061A (ja) * | 2018-08-01 | 2020-02-06 | 東レ株式会社 | 編地 |
JP7172258B2 (ja) | 2018-08-01 | 2022-11-16 | 東レ株式会社 | 編地 |
WO2023112850A1 (ja) * | 2021-12-17 | 2023-06-22 | 東レ株式会社 | ポリプロピレン短繊維 |
Also Published As
Publication number | Publication date |
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KR20180121477A (ko) | 2018-11-07 |
EP3428328A1 (en) | 2019-01-16 |
TWI775744B (zh) | 2022-09-01 |
US20190071797A1 (en) | 2019-03-07 |
JPWO2017154665A1 (ja) | 2019-01-10 |
KR102631592B1 (ko) | 2024-02-01 |
CN108779583A (zh) | 2018-11-09 |
CN108779583B (zh) | 2021-11-23 |
EP3428328A4 (en) | 2019-09-04 |
EP3428328B1 (en) | 2021-01-27 |
JP6562073B2 (ja) | 2019-08-21 |
US10793976B2 (en) | 2020-10-06 |
ES2865386T3 (es) | 2021-10-15 |
TW201800630A (zh) | 2018-01-01 |
SG11201807585YA (en) | 2018-10-30 |
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