JP7290025B2 - Dyeable polyolefin core-sheath type composite fiber and fiber structure composed thereof - Google Patents

Description

The present invention relates to dyeable polyolefin fibers. More specifically, the present invention relates to a dyeable polyolefin fiber which is excellent in light weight and is imparted with bright and deep color development, and which can be suitably employed as a fiber structure.

Polyethylene fibers and polypropylene fibers, which are types of polyolefin fibers, are excellent in light weight and chemical resistance, but have the drawback of being difficult to dye because they do not have polar functional groups. Therefore, it is not suitable for clothing applications, and is currently limited to interior applications such as tile carpets, household rugs, and automobile mats, as well as material applications such as ropes, curing nets, filter cloth, narrow tapes, braids, and chair upholstery. It is used for various purposes.

A simple dyeing method for polyolefin fibers is the addition of pigments. However, with pigments, it is difficult to stably express vivid color development and light shades like dyes, and when pigments are used, the fiber tends to be stiff, which impairs flexibility. there were.

Surface modification of polyolefin fibers has been proposed as a dyeing method that replaces pigments. For example, in Patent Document 1, an attempt is made to improve dyeability by modifying the surface of polyolefin fibers by graft copolymerization of a vinyl compound by ozone treatment or ultraviolet irradiation.

Also, a technology has been proposed to combine dyeable polymers with polyolefins having low dyeability. For example, Patent Document 2 proposes a dyeable polyolefin fiber in which polyester or polyamide is blended with polyolefin as a dyeable polymer.

Furthermore, Patent Documents 3 and 4 attempt to improve color developability by making a dyeable polymer blended with polyolefin amorphous. Specifically, in Patent Document 3, a copolymer polyester obtained by copolymerizing cyclohexanedimethanol, and in Patent Document 4, a copolymer polyester obtained by copolymerizing isophthalic acid and cyclohexanedimethanol is blended into polyolefin as a dyeable amorphous polymer. dyeable polyolefin fibers have been proposed.

JP-A-7-90783 JP-A-4-209824 Japanese Patent Publication No. 2008-533315 Japanese Patent Publication No. 2001-522947

However, the method described in Patent Document 1 requires a long period of time for ozone treatment and ultraviolet irradiation, so that the productivity is low and the barrier to industrialization is high.

In addition, in the method of Patent Document 2, although the dyeable polymer can impart coloration to the polyolefin fiber, the dyeable polymer is crystalline, so the coloration is insufficient and lacks vividness and depth. It was something. In the methods of Patent Documents 3 and 4, by making the dyeable polymer amorphous, the color developability is improved, but vividness and depth are still insufficient.

An object of the present invention is to solve the above-mentioned problems of the prior art, to provide a dyeable polyolefin fiber that can be suitably used as a fiber structure by imparting vivid and deep color development to a polyolefin fiber that is excellent in lightness. That's what it is.

The above problem of the present invention is achieved by a dyeable polyolefin core-sheath type composite fiber having a sheath component of polyolefin (A) and a core component of polymer alloy (a) comprising polyolefin (A') and highly colored polyester (B). can be resolved.

Further, two or more kinds of dicarboxylic acids are used for all the dicarboxylic acid components of the highly colored polyester (B), and the refractive index is 1.40 to 1.58 .

Furthermore, it can be suitably employed to contain a compatibilizer (C), and the compatibilizer (C) contains at least one functional group selected from an amino group and an imino group, styrene-ethylene- Butylene-styrene copolymers and/or styrene-butadiene-butylene-styrene copolymers are preferred.

The dyeable polyolefin conjugate fiber preferably has a minimum sheath thickness of 0.1 to 5.0 μm in the cross section of the fiber. It is preferable to contain 3.0 to 40.0 parts by weight of the highly colored polyester (B) with respect to a total of 100 parts by weight of B) and the compatibilizer (C).

Moreover, it can be suitably employed in a fiber structure characterized by using the dyeable polyolefin fiber as at least a part thereof.

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a dyeable polyolefin fiber which is a polyolefin fiber excellent in lightness, has excellent workability in high-order processing, is uniformly dyed, and has vivid and deep color development. can.

The dyeable polyolefin fiber of the present invention is characterized by having a core-sheath structure in which the sheath component is polyolefin (A) and the core component is polymer alloy (a) composed of polyolefin (A') and highly colored polyester (B). and

Here, the core-sheath structure in the present application means a structure in which the fiber surface is covered with a sheath component, and includes a sea-island structure in which the core has a large number of structures, that is, a multi-island structure in which the fiber surface is covered with the sheath component. .

Polymer alloy (a) has a structure in which highly colored polyester (B) is finely dispersed in polyolefin (A') as an island component. Highly colored polyester has a low refractive index, and even in polyolefin fibers, the amount of light reflected from the surface of the fiber is reduced, and light penetrates sufficiently into the interior of the fiber, giving vivid and deep color development. It refers to polyester.

The polymer alloy in the present invention means a structure in which island components are discontinuously dispersed. Here, the discontinuity of the island component means that the island component has an appropriate length, and the cross section perpendicular to the fiber axis, that is, the cross section of the fiber has a sea-island structure at any interval within the same single filament. are different in shape. Discontinuity of the island component in the present invention can be confirmed by the method described in Examples. When the island components are discontinuously dispersed, the island components have a spindle shape, and thus the efficiency of color development by the light transmitted through the island components is improved, the clarity is improved, and deep color development is obtained. As described above, the polymer alloy fiber in the present invention includes a core-sheath composite fiber in which one island is continuous in the fiber axis direction and has the same shape, and a plurality of islands are continuous in the fiber axis direction and have the same shape. It is essentially different from the sea-island composite fiber. Such a polymer alloy fiber can be obtained, for example, by molding a polymer alloy composition formed by kneading a polyolefin (A') and a highly colored polyester (B) at any stage before the completion of melt spinning. can be done.

The dyeable polyolefin fiber of the present invention preferably has a minimum sheath thickness of 0.1 to 5.0 μm in the cross section of the fiber. Here, the minimum thickness of the sheath in the fiber cross section refers to the shortest distance from the fiber surface to the highly colored polyester (B) component. If the minimum thickness of the sheath in the cross section of the fiber is 0.1 μm or more, the highly colored polyester (B) is not exposed on the fiber surface, which is preferable because the workability in high-order processing is stabilized. In addition, if it is 5.0 μm or less, incident light from the fiber surface can sufficiently reach the highly colored polyester (B), and vivid and deep color development can be exhibited, so it is preferable, and it is 3.0 μm or less. is more preferable, and 2.0 μm or less is even more preferable.

The cross-sectional shape of the dyeable polyolefin fiber of the present invention is not particularly limited, and can be appropriately selected according to the application and required properties. There may be. Examples of non-circular cross-sections include, but are not limited to, multi-lobed, polygonal, flattened, elliptical, and the like. Moreover, the composite form may be a core-sheath cross-section, and may be a sea-island cross-section in which the number of constituents of the core is large, that is, the fiber surface is coated with a sheath component. In the case of a core-sheath cross-section or a sea-island cross-section, there is no particular limitation on the shape of the core component in the cross-section of the fiber, and it may be a perfect circular cross-section or a non-circular cross-section. Examples of non-circular cross-sections include, but are not limited to, multi-lobed, polygonal, flattened, elliptical, and the like.

By disposing the highly color-developing polyester (B) having two or more dicarboxylic acids as constituent components in the polyolefin (A') as a dyeable polymer, it is possible to impart color-developing properties to the polyolefin (A'). . In addition, by bringing the refractive index of the highly colored polyester (B) closer to that of the polyolefins (A) and (A'), the efficiency of color development by transmitted light is improved, and vivid and deep color development can be achieved. Furthermore, by coating the polymer alloy (a) with the polyolefin (A), excellent operational stability in high-order processing, and by not exposing the highly colored polyester (B) on the surface, uniform color development can be achieved. I can expect it.

The component constituting the sheath of the dyeable polyolefin fiber of the present invention is polyolefin (A), and the sea component in the core component polymer alloy (a) is polyolefin (A'). Since polyolefin has a low specific gravity, it is possible to obtain fibers excellent in lightness. Polyolefins (A) and (A') include, but are not limited to, polyethylene, polypropylene, polybutene-1, polymethylpentene, and the like. Among them, polypropylene is preferable because it has 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. In addition, polypropylene is particularly suitable for use in clothing. In this case, since the fiber surface is polypropylene, water repellency and heat retention can be imparted to the fiber itself.

The polyolefins (A) and (A') of the present invention may be homopolymers or copolymers with other α-olefins. One or two or more other α-olefins (hereinafter sometimes simply referred to as α-olefins) may be copolymerized.

The α-olefin preferably has 2 to 20 carbon atoms, and the molecular chain of the α-olefin may be linear or branched. Specific examples of α-olefins 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, 3-ethyl-1-hexene, and the like.

The copolymerization rate of α-olefin is preferably 20 mol % or less. If the copolymerization rate of the α-olefin is 20 mol % or less, it is preferable because a dyeable polyolefin fiber having good mechanical properties and heat resistance can be obtained. The copolymerization rate of the α-olefin is more preferably 15 mol % or less, still more preferably 10 mol % or less.

The island component in the polymer alloy (a) that constitutes the core component of the dyeable polyolefin fiber of the present invention is highly colored polyester (B) containing two or more dicarboxylic acids as constituent components.

The highly colored polyester (B) of the present invention is preferably copolymerized with two or more dicarboxylic acids. Specific examples of dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, and 1,2-cyclohexanedicarboxylic acid. , 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 3 ,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, aromatic dicarboxylic acids such as anthracenedicarboxylic 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-cyclohexanedicarboxylic acid, dimer Aliphatic dicarboxylic acids such as acids, aromatic diols such as catechol, naphthalene diol, bisphenol, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, cyclohexanedimethanol These include, but are not limited to, aliphatic diols such as

As a method for improving the coloring property of fibers, lowering the refractive index of the polymer constituting the fiber and lowering the crystallinity of the polymer can be mentioned, but lowering the refractive index of the polymer has a higher effect. can be obtained.

When the refractive index of the polymer composing the fiber is lowered, the amount of light reflected from the surface of the fiber is reduced, and the light penetrates sufficiently into the interior of the fiber, thereby imparting vivid and deep color development. In addition, since the dye is less likely to be absorbed by the crystalline portion and more likely to be absorbed by the amorphous portion, the lower the crystallinity of the polymer, the more preferable it is, in order to improve the color developability. preferable. For example, in the methods described in Patent Literatures 3 and 4, an attempt is made to impart coloring properties to polyolefin fibers by combining amorphous copolyester obtained by copolymerizing cyclohexanedimethanol with polyolefin.

The highly colored polyester (B) of the present invention preferably has a refractive index of 1.40 to 1.58. If the refractive index of the highly colored polyester (B) is 1.58 or less, the refractive index of the highly colored polyester (B) is close to the refractive index of the polyolefin, and even in the polyolefin fiber, the reflected light from the fiber surface is small. It is preferable because it allows light to sufficiently penetrate into the interior of the fiber and imparts vivid and deep color development. More preferably, the highly colored polyester (B) has a refractive index of 1.56 or less.

In the dyeable polyolefin fiber of the present invention, the polymer alloy (a) of the core component is a total of 100 parts by weight of the polyolefin (A') and the highly colored polyester (B), and the highly colored polyester (B) is added at 3.0 parts by weight. It is preferable to contain up to 40.0 parts by weight. If the content of the highly color-developing polyester (B) is 3.0 parts by weight or more, the copolymer polyester (B) having a low refractive index and high color-developing property is dispersed in the polyolefin (A') having a low refractive index. Therefore, it is preferable because vivid and deep color development can be realized. The content of the highly colored ester (B) is more preferably 3.5 parts by weight or more, and even more preferably 4.0 parts by weight or more. On the other hand, if the content of the highly colored polyester (B) is 40.0 parts by weight or less, the highly colored polyester (B) present in large numbers in the polyolefin (A′) is dyed to allow light transmitted to the island component. It is preferable because the efficiency of color development by is improved and vivid and deep color development can be obtained. It is also preferable because it does not impair the lightness of polyolefins (A) and (A'). The content of the highly colored polyester (B) is more preferably 35.0 parts by weight or less, even more preferably 30.0 parts by weight or less.

In the present invention, the dispersibility of the highly colored polyester (B) in the polyolefin (A') in the polymer alloy (a) constituting the core component is improved, the dispersion state is controlled, and the interfacial adhesion between the sea component and the island component is improved. For the purpose of improvement, a compatibilizer (C) may be added as necessary. In addition, when a sea-island structure is formed by melt spinning, a bulge called ballast occurs directly under the spinneret, and the thinning deformation of the fiber tends to become unstable. A compatibilizing agent (C) may be used for the purpose of improving spinning operability and obtaining fibers with small fineness unevenness and excellent uniformity in the longitudinal direction of the fibers.

The compatibilizing agent (C) in the present invention can be appropriately selected according to the composite ratio of the polyolefin (A') and the highly colored polyester (B). The compatibilizing agent (C) may be used alone or in combination of two or more.

As the compatibilizing agent (C) in the present invention, a hydrophobic component having a high affinity with the polyolefin (A') in the polymer alloy (a) constituting the core component and a functional component having a high affinity with the highly colored polyester (B) Compounds in which both groups are contained within a single molecule are preferred. Alternatively, the hydrophobic component having a high affinity for the polyolefin (A') in the polymer alloy (a) constituting the highly hydrophobic core component and the functional group capable of reacting with the highly colored polyester (B) are both single. A compound contained in one molecule can be preferably employed.

Specific examples of the hydrophobic component constituting the compatibilizer (C) include polyolefin resins such as polyethylene, polypropylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; styrene resins such as polystyrene; Polymer, ethylene-butylene copolymer, propylene-butylene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, styrene-ethylene- Conjugated diene-based resins such as propylene-styrene copolymers and styrene-butadiene-butylene-styrene copolymers are included, but are not limited to these.

Specific examples of the functional group having high affinity with the highly colored polyester (B) or the functional group capable of reacting with the highly colored polyester (B), which constitute the compatibilizer (C), include an acid anhydride group, a carboxyl group, Examples include, but are not limited to, hydroxyl groups, epoxy groups, amino groups and imino groups. Among them, an amino group and an imino group are preferred because of their high reactivity with the highly colored polyester (B).

Specific examples of the compatibilizer (C) include maleic acid-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified polymethylpentene, epoxy-modified polypropylene, epoxy-modified polystyrene, and maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer. Polymers, maleic anhydride-modified styrene-butadiene-butylene-styrene copolymers, amine-modified styrene-ethylene-butylene-styrene copolymers, amine-modified styrene-butadiene-butylene-styrene copolymers, imine-modified styrene-ethylene- Examples include butylene-styrene copolymers, imine-modified styrene-butadiene-butylene-styrene copolymers, but are not limited to these.

The compatibilizing agent (C) in the present invention is a polyolefin resin, acrylic It is preferably one or more compounds selected from resins, styrene resins and conjugated diene resins. Among them, a styrene-ethylene-butylene-styrene copolymer or a styrene-butadiene-butylene-styrene copolymer containing at least one functional group selected from an amino group and an imino group is a highly colored polyester (B ) and is highly effective in improving the dispersibility of the highly colored polyester (B) in the polyolefin (A′). It is preferable because the efficiency of color development by light transmitted through the component is improved, and vivid and deep color development can be obtained.

When the compatibilizer (C) is added, the dyeable polyolefin fiber of the present invention contains the polyolefin (A') in the polymer alloy (a) constituting the core component, the highly colored polyester (B), the compatibilizer ( It is preferable to contain 0.1 to 10.0 parts by weight of the compatibilizing agent (C) with respect to 100 parts by weight of C) in total. When the content of the compatibilizing agent (C) is 0.1 parts by weight or more, the effect of compatibilizing the polyolefin (A') and the highly colored polyester (B) can be obtained, so that the dispersion diameter of the island component becomes small. is preferable because aggregation of the dye compound can be suppressed to bring the dye compound closer to monodispersion, color development efficiency is improved, and vivid and deep color development can be obtained. In addition, it is preferable because it is possible to obtain a fiber with small fineness unevenness and excellent uniformity in the longitudinal direction of the fiber while improving the spinning operation such as suppression of yarn breakage. The content of the compatibilizer (C) is more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more. On the other hand, if 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 copolymer polyester (B) that constitute the dyeable polyolefin fiber can be maintained. In addition, it is preferable because destabilization of spinning operability 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, even more preferably 5.0 parts by weight or less.

The dyeable polyolefin fibers of the present invention preferably contain an antioxidant. Containing an antioxidant not only suppresses oxidative decomposition of polyolefin due to long-term storage or tumbler drying, but also improves the durability of fiber properties such as mechanical properties, which is preferable.

The antioxidant in the present invention is preferably a phenolic compound, a phosphorus compound, a sulfur compound, or a hindered amine compound. These antioxidants may be used alone or in combination of two or more.

The phenolic compound in the present invention is a radical chain reaction inhibitor having a phenolic structure, and may be used alone or in combination of two or more. Among them, pentaerythritol-tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenol)propionate) (eg Irganox 1010 manufactured by BASF), 2,4,6-tris(3′,5′- di-t-butyl-4′-hydroxybenzyl)mesitylene (for example, Adekastab AO-330 manufactured by ADEKA), 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4- Hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecane (for example, Sumitomo Chemical Sumilizer GA-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, THANOX1790 manufactured by Tokyo Kasei Kogyo Co., Ltd. can be preferably used because of its high oxidative decomposition suppressing effect.

The phosphorus-based compound in the present invention is a phosphorus-based antioxidant that reduces peroxides without generating radicals and is itself oxidized, and may be used alone or in combination of two or more. may Among them, tris(2,4-di-t-butylphenyl) phosphite (eg Irgafos168 manufactured by BASF), 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2 ,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (for example, Adekastab PEP-36 manufactured by ADEKA) is highly effective in suppressing oxidative decomposition and can be suitably used.

The sulfur-based compound in the present invention is a sulfur-based antioxidant that reduces peroxides without generating radicals and is itself oxidized, and may be used alone or in combination of two or more. may

The hindered amine-based compound in the present invention is a hindered amine-based antioxidant that has the effect of scavenging radicals generated by ultraviolet rays or heat and functioning as an antioxidant to regenerate deactivated phenol-based antioxidants. may be used alone, or two or more thereof may be used in combination. Among them, an amino ether hindered amine compound or a high molecular weight hindered amine compound having a molecular weight of 1,000 or more can be preferably used. Amino ether-type hindered amine compounds are preferable because they have low basicity and can suppress yellowing of fibers caused by nitrogen oxide gas during long-term storage. Specific examples of amino ether type hindered amine compounds include bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (e.g., Adekastab LA-81 manufactured by ADEKA), bisdecanedioate [ 2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] (eg Tinuvin PA123 manufactured by BASF), etc., but not limited thereto. Further, a high molecular weight hindered amine compound having a molecular weight of 1000 or more is preferable because it can suppress elution from inside the fiber due to washing or cleaning using an organic solvent. A specific example of a high molecular weight hindered amine compound having a molecular weight of 1000 or more is 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-hexanediyl (2,2,6,6-tetramethyl-4-piperidinyl)imino)) (for example, manufactured by BASF CHIMASSORB944), dibutylamine-1,3,5-triazine-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2, Polycondensates of 2,6,6-tetramethyl-4-piperidyl)butylamine (eg, CHIMASSORB2020 manufactured by BASF) and the like, but are not limited thereto.

The content of the antioxidant in the dyeable polyolefin fiber of the present invention is 0.00 per 100 parts by weight in total of the polyolefins (A) and (A'), the highly colored polyester (B) and the compatibilizer (C). It is preferably 1 to 5.0 parts by weight. If the content of the antioxidant is 0.1 parts by weight or more, the effect of suppressing oxidative decomposition can be imparted to the fibers, which is preferable. The content of the antioxidant is more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more. On the other hand, when the content of the antioxidant is 5.0 parts by weight or less, the color tone of the fiber does not deteriorate 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 fibers of the present invention may be modified in various ways by adding secondary additives. Specific examples of secondary additives include plasticizers, ultraviolet absorbers, infrared absorbers, fluorescent whitening agents, mold release agents, antibacterial agents, nucleating agents, heat stabilizers, antistatic agents, anticoloring agents, and adjusting agents. agents, matting agents, defoamers, preservatives, gelling agents, latexes, fillers, inks, colorants, dyes, pigments, perfumes, and the like. These secondary additives may be used alone or in combination of two or more.

The fineness of the multifilament of the dyeable polyolefin fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required properties, but is preferably 10 to 3000 dtex. The fineness in the present invention refers to the value measured by the method described in Examples. If the fineness of the dyeable polyolefin fiber is 10 dtex or more, it is preferable because there is less yarn breakage, good processability, less fuzz during use, and excellent durability. The fineness of the dyeable polyolefin fibers is more preferably 30 dtex or more, still more preferably 50 dtex or more. On the other hand, if the fineness of the dyeable polyolefin fiber is 3000 dtex or less, it is preferable because the flexibility of the fiber and the fiber structure is not impaired. The fineness of the dyeable polyolefin fibers is more preferably 2500 dtex or less, even more preferably 2000 dtex or less.

The single filament 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 properties, but is preferably 0.5 to 20 dtex. The single yarn fineness in the present invention refers to the value obtained by dividing the fineness measured by the method described in the Examples by the number of single yarns. If the single filament 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 occurrence of fluff is small during use, and the durability is excellent. The single filament fineness of the dyeable polyolefin fibers is more preferably 0.6 dtex or more, still more preferably 0.8 dtex or more. On the other hand, if the single filament 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 filament fineness of the dyeable polyolefin fibers is more preferably 15 dtex or less, even more 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 application and required properties. is preferred. The strength in the present invention refers to the value measured by the method described in Examples. If the strength of the dyeable polyolefin fiber is 1.0 cN/dtex or more, it is preferable because the occurrence of fluff during use is small and the durability is excellent. The strength of the dyeable polyolefin fiber is more preferably 1.5 cN/dtex or more, still more preferably 2.0 cN/dtex or more. On the other hand, if the strength of the dyeable polyolefin fiber is 6.0 cN/dtex or less, it is preferable because the flexibility of the fiber and the fiber structure is not impaired.

The elongation of the dyeable polyolefin fiber of the present invention is not particularly limited and can be appropriately selected according to the application and required properties, but from the viewpoint of durability, it is preferably 10 to 60%. The elongation in the present invention refers to a value measured by the method described in Examples. When the elongation of the dyeable polyolefin fiber is 10% or more, the abrasion resistance of the fiber and the fiber structure is improved, less fluff is generated during use, and the durability is improved, which is preferable. The elongation of the dyeable polyolefin fibers is more preferably 15% or more, and even more preferably 20% or more. On the other hand, if the elongation of the dyeable polyolefin fiber is 60% or less, the dimensional stability of the fiber and the fiber structure is improved, which is preferable. The elongation of the dyeable polyolefin fibers is more preferably 55% or less, and even more preferably 50% or less.

The fineness fluctuation 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 Examples. The fineness fluctuation value U% is an index of thickness unevenness in the longitudinal direction of the fiber, and the smaller the fineness fluctuation value U%, the smaller the thickness unevenness 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, uniform dyeability, and color development, but 0.1% is the lower limit of the manufacturable range. On the other hand, if the fineness fluctuation value U% (hi) of the dyeable polyolefin fiber is 1.5% or less, the uniformity in the longitudinal direction of the fiber is excellent, fluff and yarn breakage are unlikely to occur, and the dyeing is performed. It is preferable because defects such as uneven dyeing and streaks in dyeing hardly occur in the process, and a fiber structure excellent in uniform dyeing property and coloring property can be obtained. The fineness fluctuation 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 dispersion diameter of the highly colored polyester (B) in the fiber cross section of the dyeable polyolefin fiber of the present invention is 30 to 1000 nm. In the present invention, the dispersion diameter of the island component in the cross section of the fiber refers to the value measured by the method described in Examples. When the highly colored polyester (B) has a dispersion diameter of 30 nm or more in the cross section of the fiber, the dye is firmly incorporated into the copolymerized polyester (B) in the polymer alloy (a) constituting the core component, and permeates to the island component. The efficiency of color development by the light is improved, and vivid and deep color development can be realized. On the other hand, if the dispersed diameter of the island component in the cross section of the fiber is 1000 nm or less, the specific interfacial area of the sea-island interface can be made sufficiently large, so that interfacial peeling and abrasion caused by this can be suppressed, and uniform dyeing can be achieved. Excellent in color development properties. In addition, the smaller the dispersion diameter of the island component, the more the dye compound can be suppressed from aggregating and the dye compound can be brought closer to monodispersion, thereby improving the color development efficiency. Therefore, the dispersed diameter of the island component in the cross section of the fiber is preferably 700 nm or less, more preferably 500 nm or less, and particularly preferably 300 nm or less.

The specific gravity of the dyeable polyolefin fiber of the present invention is preferably 0.83-1.0. The specific gravity in the present invention refers to the value measured by the method described in Examples, and is the true specific gravity. When the fiber has a hollow portion, the apparent specific gravity becomes smaller even if the true specific gravity is the same, and the value of the apparent specific gravity changes according to the hollow ratio. Polyolefins have a low specific gravity, for example polymethylpentene has a specific gravity of 0.83 and polypropylene has a specific gravity of 0.91. When polyolefin is made into fibers alone, it is possible to obtain fibers excellent in lightness, but there is a drawback that it cannot be dyed. In the present invention, a polyolefin fiber having a low specific gravity and a polymer alloy fiber composed of a dyeable copolymer polyester can be used to impart color developability to the polyolefin fiber, which is excellent in lightness. The specific gravity of the dyeable polyolefin fiber varies depending on the specific gravity of the highly color-developing polyester (B) to be combined, the compounding ratio of the highly color-developing polyester (B), and the like. The specific gravity of the dyeable polyolefin fiber is preferably as low as possible from the viewpoint of lightness, and is preferably 1.0 or less. If the specific gravity of the dyeable polyolefin fiber is 1.0 or less, it is possible to achieve both lightness due to the polyolefins (A) and (A') and color development due to the high color development polyester (B), which is preferable. More preferably, the specific gravity of the dyeable polyolefin fiber is 0.98 or less.

The dyeable polyolefin fibers of the present invention are not particularly limited in fiber form, and may be in any form such as monofilament, multifilament and staple.

The dyeable polyolefin fibers of the present invention can be subjected to processing such as false twisting and twisting in the same manner as ordinary fibers, and can be woven and knitted in the same manner as ordinary fibers.

The form of the fiber structure composed of the dyeable polyolefin fibers of the present invention is not particularly limited, and can be made into woven fabric, knitted fabric, pile fabric, non-woven fabric, spun yarn, wadding, etc. according to known methods. Further, the fiber structure composed of the dyeable polyolefin fibers of the present invention may be of any woven structure or knitted structure, such as plain weave, twill weave, satin weave, or variations thereof, warp knitting, weft knitting, circular knitting. , lace knitting, or variations of these knitting can be suitably employed.

When forming a fiber structure, the dyeable polyolefin fiber of the present invention may be combined with other fibers by mixed weaving or mixed knitting, or the fiber structure may be formed after making a mixed yarn with other fibers. .

Next, the method for producing the dyeable polyolefin fiber of the present invention is shown below.

As a method for producing the dyeable polyolefin fiber of the present invention, a known melt spinning method, drawing method, and false twisting method can be used.

In the present invention, the polyolefins (A) and (A'), the highly colored polyester (B), and the compatibilizer (C) are dried before melt spinning to a moisture content of 0.3% by weight or less. preferable. A water content of 0.3% by weight or less is preferable because foaming due to moisture does not occur during melt spinning, and spinning can be stably performed. It is also 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 even more preferably 0.1% by weight or less.

When core-sheath type conjugate spinning is performed, examples of the method of extruding from a spinneret to form a fiber thread include, but are not limited to, the following examples. As a first example, polyolefin (A′) and highly colored polyester (B) are melt-kneaded in advance by an extruder or the like to form a polymer alloy (a) constituting the core component. , polyolefin (A) and chips are supplied to separate melt spinning machines and melted separately, and are metered by metering pumps. After that, it is introduced into a heated spinning pack in the spinning block, the molten polymer is filtered in the spinning pack, and then the polymer is merged so as to have the desired cross section, and is discharged from the spinneret to form a fiber thread. is mentioned. As a second example, after drying the chips as necessary and mixing the polyolefin (A') and the highly colored polyester (B) in the state of chips, the polyolefin (A) and the chips are transferred to separate melt spinning machines. Feed and melt separately and meter with a metering pump. After that, it is introduced into a heated spinning pack in the spinning block, the molten polymer is filtered in the spinning pack, and then the polymer is merged so as to have the desired cross section, and is discharged from the spinneret to form a fiber thread. is mentioned.

The fibrous yarn discharged from the spinneret is cooled and solidified by a cooling device, taken up by a first godet roller, and wound by a winder via a second godet roller to obtain a wound yarn. In order to improve spinning operability, productivity and mechanical properties of fibers, a heating cylinder or a heat retaining cylinder having a length of 2 to 20 cm may be installed under the spinneret as necessary. Alternatively, the fiber yarn may be lubricated using an oil supply device, or the fiber yarn may be entangled using an entangling device.

The spinning temperature in the melt spinning can be appropriately selected according to the melting point and heat resistance of the polyolefins (A) and (A'), the highly colored polyester (B), and the compatibilizer (C). °C is preferred. When the spinning temperature is 220° C. or higher, the elongation viscosity of the fibrous yarn extruded from the spinneret is sufficiently lowered to stabilize the expulsion. It is preferable because it can The spinning temperature is more preferably 230°C or higher, even more preferably 240°C or higher. On the other hand, if the spinning temperature is 320° C. or lower, thermal decomposition during spinning can be suppressed, and deterioration in mechanical properties and coloring of the resulting dyeable polyolefin fiber can be suppressed, which is preferable. The spinning temperature is more preferably 300°C or lower, and even more preferably 280°C or lower.

The spinning speed in the melt spinning can be appropriately selected depending on the content of the highly colored polyester (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 process is more preferably 1000 m/min or more, and even more preferably 1500 m/min or more. On the other hand, if the spinning speed is 6000 m/min or less, it is preferable because the spinning tension can be suppressed and the spinning can be stably performed without yarn breakage. The spinning speed in the two-step process is more preferably 4500 m/min or less, and even more preferably 4000 m/min or less. In the case of a one-step method in which spinning and drawing are simultaneously performed without once winding, the spinning speed is preferably 500 to 5000 m/min for the low speed roller and 2500 to 6000 m/min for the high speed roller. If the low-speed roller and the high-speed roller are within the above range, the running yarn is stabilized, yarn breakage can be suppressed, and stable spinning can be performed, which is preferable. In the one-step method, the spinning speed is more preferably 1000 to 4500 m/min for the low speed roller and 3500 to 5500 m/min for the high speed roller.

When drawing is performed by a one-step method or a two-step method, either a one-step drawing method or a multi-step drawing method with two or more steps may be used. A heating method for drawing is not particularly limited as long as it is an apparatus capable of directly or indirectly heating the running yarn. Specific examples of heating methods include, but are not limited to, heating rollers, hot pins, hot plates, liquid baths such as hot water and hot water, gas baths such as hot air and steam, and lasers. These heating methods may be used alone or in combination. From the viewpoint of controlling the heating temperature, uniformly heating the running yarn, and not complicating the equipment, the heating method includes contact with a heating roller, contact with a hot pin, contact with a hot plate, and immersion in a liquid bath. It can be preferably adopted.

The drawing temperature when drawing is appropriately determined according to the melting points of the polyolefins (A) and (A'), the highly colored polyester (B), and the compatibilizer (C), and the strength and elongation of the fibers after drawing. Although it can be selected, it is preferably 20 to 150°C. If the drawing temperature is 20° C. or higher, the thermal deformation of the yarn supplied for drawing becomes uniform during drawing, the occurrence of fineness unevenness can be suppressed, and a fiber excellent in uniformity in the longitudinal direction of the fiber can be obtained. It is preferable because On the other hand, if the drawing temperature is 150° C. or less, fusion between fibers and thermal decomposition due to contact with the heating roller can be suppressed, and process passability, uniform dyeability, and color development are favorable, which is preferable. . Moreover, since the slipperiness|lubricacy of a fiber with respect to a drawing roller becomes favorable, yarn breakage is suppressed and stable drawing can be performed, and it is preferable. The stretching temperature is more preferably 145° C. or lower, even more preferably 140° C. or lower. Also, heat setting at 60 to 150° C. may be performed as necessary.

The draw ratio in the case of drawing can be appropriately selected according to the elongation of the fiber before drawing and the strength and elongation of the fiber after drawing, but it should be 1.02 to 7.0 times. is preferred. A draw ratio of 1.02 times or more is preferable because the mechanical properties such as strength and elongation of the fiber can be improved by drawing. The draw ratio is more preferably 1.2 times or more, and still more preferably 1.5 times or more. On the other hand, if the draw ratio is 7.0 times or less, yarn breakage during drawing is suppressed, and stable drawing can be performed, which is preferable. The draw ratio is more preferably 6.0 times or less, and even more preferably 5.0 times or less.

The drawing speed in drawing can be appropriately selected depending on whether the drawing method is a one-step method or a two-step method. In the case of the one-step process, the speed of the high speed rollers at the above spinning speed corresponds to the drawing speed. The drawing speed in the two-step drawing is preferably 30 to 1000 m/min. A drawing speed of 30 m/min or more is preferable because the running yarn is stabilized and yarn breakage can be suppressed. When stretching is performed by a two-step method, the stretching speed is more preferably 50 m/min or more, and still more preferably 100 m/min or more. On the other hand, if the drawing speed is 1000 m/min or less, yarn breakage during drawing can be suppressed and stable drawing can be performed, which is preferable. When stretching is performed by a two-step method, the stretching speed is more preferably 900 m/min or less, and even more preferably 800 m/min or less.

In the case of false twisting, so-called bulerier processing, in which both a one-stage heater and a two-stage heater are used, can be appropriately selected in addition to so-called wooly processing, in which only one-stage heater is used.

As devices used for false twisting, FR (feed roller), 1DR (1 draw roller) heater, cooling plate, false twisting device, 2DR (2 draw rollers), 3DR (3 draw rollers), entangling nozzle, 4DR ( 4 draw rollers), a false twisting device with a winder.

The processing ratio between FR and 1DR can be appropriately selected according to the elongation of the fiber used for false twisting and the elongation of the fiber after false twisting, but it is preferably 1.0 to 2.0 times. .

The heating method of the heater may be either contact type or non-contact type. The heater temperature varies depending on the melting points of polyolefin (A), polyester (B), styrene-ethylene-butylene-styrene copolymer and/or styrene-butadiene-butylene-styrene copolymer (C), and fibers after false twisting. It is preferable that the heater temperature is 90° C. or higher in the case of the contact type, and the heater temperature is 150° C. or higher in the case of the non-contact type. If the heater temperature is 90° C. or higher in the case of the contact type or 150° C. or higher in the case of the non-contact type, the yarn supplied to the false twisting process is sufficiently preheated, and the heat associated with drawing is reduced. It is preferable because the deformation becomes uniform, the occurrence of fuzz and fineness unevenness can be suppressed, and high-quality fibers and fiber structures with excellent uniformity in the fiber longitudinal direction and excellent level dyeing can be obtained. In the case of the contact type, the heater temperature is more preferably 100° C. or higher, more preferably 110° C. or higher. In the non-contact type, the heater temperature is more preferably 200° C. or higher, more preferably 250° C. or higher. The upper limit of the heater temperature may be a temperature at which undrawn yarn or drawn yarn used for false twisting is not fused in the heater.

The false twisting device is preferably a friction false twisting type, and includes, but is not limited to, a friction disk type, a belt nip type, and the like. Among them, the friction disk type is preferable, and by configuring all the disk materials of ceramics, the false twisting can be stably performed even when the operation is performed for a long period of time. The ratio between 2DR and 3DR and between 3DR and 4DR can be appropriately selected according to the strength and elongation of the fiber after false twisting, but is preferably 0.9 to 1.0. Between 3DR and 4DR, entangling may be imparted using an entangling nozzle or additional oil may be applied using an oiling guide in order to improve process passability of the fibers after false twisting.

The processing speed for false twisting can be selected as appropriate, but is preferably 200 to 1000 m/min. A processing speed of 200 m/min or more is preferable because the running yarn is stable and yarn breakage can be suppressed. The processing speed is more preferably 300 m/min or higher, even more preferably 400 m/min or higher. On the other hand, if the processing speed is 1000 m/min or less, yarn breakage during false twisting is suppressed, and stable false twisting can be performed, which is preferable. The processing speed is more preferably 900 m/min or less, even more preferably 800 m/min or less.

In the present invention, any state of the fiber or fiber structure may be dyed as required. In the present invention, disperse dyes can be preferably used as dyes. The polyolefins (A) and (A') constituting the dyeable polyolefin fiber are hardly dyed, but the dyeing of the highly color-developing polyester (B) results in vivid and deep color development. And it becomes possible to obtain a fiber structure.

The dyeing method in the present invention is not particularly limited, and cheese dyeing machines, jet dyeing machines, drum dyeing machines, beam dyeing machines, jiggers, high-pressure jiggers and the like can be preferably employed according to known methods.

In the present invention, there are no particular restrictions on dye concentration and dyeing temperature, and known methods can be suitably employed. Further, if necessary, scouring may be performed before dyeing, and reduction cleaning may be performed after dyeing.

The dyeable polyolefin fiber of the present invention and the fiber structure comprising the same are obtained by imparting brilliant and deep color development to the polyolefin fiber which is excellent in lightness. Therefore, in addition to applications in which conventional polyolefin fibers are used, it can be applied to clothing applications and applications requiring lightness and color development. Applications in which conventional polyolefin fibers are used include interior applications such as tile carpets, household rugs, and automobile mats; Examples include, but are not limited to, material applications such as width tapes, braids, and upholstery. Furthermore, applications expanded by the present invention include general clothing such as women's clothing, men's clothing, linings, underwear, down jackets, vests, innerwear, and outerwear, and sports clothing such as windbreakers, outdoor wear, skiwear, golf wear, and swimwear. , futon linings, futon covers, blankets, blanket linings, blanket covers, pillowcases, bedding such as sheets, tablecloths, curtains and other interior materials, belts, bags, sewing threads, sleeping bags, materials such as tents, etc. include, but are not limited to.

The present invention will be described in more detail below with reference to examples. Each characteristic value in the examples was obtained by the following method.

A. Refractive index 1 g of polymer of polyolefin (A) or (A') vacuum-dried in advance or highly colored polyolefin (B) was used as a sample, and pressed using a 15TON 4-column single-action lift press machine manufactured by Gonno Hydraulic Machinery Works. A film was produced. The sample and a spacer with a thickness of 50 μm are sandwiched between infusible polyimide films (Kapton 200H manufactured by Toray DuPont), inserted into a press, melted at 230° C. for 2 minutes, and then pressed at a pressure of 2 MPa for 1 minute. Then, it was quickly removed from the press and quenched in water at 20°C to obtain a press film with a thickness of 50 µm. Subsequently, JIS K0062:1992 (Method for measuring the refractive index of chemical products)6. The refractive index of the press film was measured according to the method for measuring the film sample described in . In an environment with a temperature of 20 ° C. and a humidity of 65% RH, Elma's Abbe refractometer ER-1 type, monobromonaphthalene (nD = 1.66) as an intermediate liquid, and a test piece (nD = 1.74) as a glass piece. Measurement was performed three times per sample, and the average value was taken as the refractive index.

B. Polymer alloy composite ratio Regarding the polymer alloy (a) as the core component of the dyeable polyolefin fiber, the total of the polyolefin (A') and the highly colored polyester (B) used as raw materials is 100 parts by weight, and the composite ratio is (A' )/(B) [parts by weight] is the total of 100 parts by weight of the polyolefin (A′), the highly colored polyester (B), and the compatibilizer (C) used as raw materials, and the composite ratio is (A′)/ (B)/(C) [parts by weight] was calculated.

C. Core-Sheath Composite Ratio A core/sheath composite ratio (weight ratio) was calculated from the weight of the sheath component and the weight of the core component used as raw materials for the core-sheath type composite fiber.

D. Fineness 100 m of the fiber obtained in the example was weighed using an INTEC electric measuring machine in an environment of a temperature of 20°C and a humidity of 65% RH. The weight of the obtained skein was measured, and the fineness (dtex) was calculated using the following formula. The measurement was performed 5 times for each sample, and the average value was taken as the fineness.
Fineness (dtex) = weight (g) of 100m of fiber x 100.

E. 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. Tensilon UTM-III-100 type manufactured by Orientec was used to conduct a tensile test under the conditions of an initial sample length of 20 cm and a tensile speed of 20 cm/min in an environment of a temperature of 20° C. and a humidity of 65% RH. The stress (cN) at the point indicating the maximum load is divided by the fineness (dtex) to calculate the strength (cN/dtex), and the elongation (L1) at the point indicating the maximum load and the initial sample length (L0) are used as follows. The elongation (%) was calculated by the formula. In addition, the measurement was performed 10 times for each sample, and the average value was used as the strength and the elongation.
Elongation (%) = {(L1-L0)/L0} x 100.

F. Fineness fluctuation value U% (hi)
The fineness fluctuation value U% (hi) is obtained by using the fiber obtained in the example as a sample, using a Wooster tester 4-CX manufactured by Zellweger Wooster, measuring speed 200 m / min, measuring time 2.5 minutes, measuring fiber length U% (half inert) was measured under the conditions of 500 m and a twist number of 12000/m (S twist). The measurement was performed 5 times for each sample, and the average value was taken as the fineness fluctuation value U% (hi).

G. Sheath Thickness Fibers obtained according to the examples were embedded in epoxy resin, frozen in a Reichert FC 4E cryosectioning system, and cut with a Reichert-Nissei ultracut N (ultramicrotome) equipped with a diamond knife. After that, the cut surface, that is, the cross section of the fiber was observed with a transmission electron microscope (TEM) H-7100FA manufactured by Hitachi, Ltd. at a magnification of 1000 to take a micrograph of the cross section of the fiber. Randomly extract 10 single yarns from the obtained photograph, and use image processing software (WINROOF manufactured by Mitani Shoji Co., Ltd.) to measure the distance from the contour of the fiber cross section to the closest highly colored polyester (B) in each single yarn. The distance was obtained, and the average value was taken as the sheath thickness T (nm).

H. Dispersion Diameter of Highly Color-Developing Polyester (B), Discontinuity of Highly Color-Developing Polyester (B) Microscopic photographs of fiber cross sections were taken in the same manner as the microscopic photography described in G above. Observation was performed at magnifications of 300, 500, 1,000, 3,000, 5,000, 10,000, 30,000, and 50,000 times. The lowest magnification at which the island component made of highly colored polyester (B) can be observed was selected. The diameter of the island component composed of highly colored polyester (B) in 100 polymer alloys (a) randomly selected from the same photograph was measured using image processing software (WINROOF manufactured by Mitani Shoji Co., Ltd.). , and the average value thereof was taken as the dispersion diameter (nm) of the highly colored polyester (B). Since the island component present in the cross section of the fiber is not necessarily a perfect circle, the diameter of the circumscribed circle was used as the dispersion diameter of the island component when the circle was not perfect.

When the number of island components composed of the highly colored polyester (B) in the polymer alloy (a) present in the fiber cross section of the single yarn is less than 100, a plurality of single yarns produced under the same conditions are used as samples, and the fiber cross section is measured. observed. When taking micrographs, the highest magnification that allows observation of the entire single filament was selected. Regarding the photographs taken, the dispersion diameter of the island component composed of the highly colored polyester (B) in the polymer alloy (a) present in the fiber cross section of each single yarn was measured, and a total of 100 pieces in the polymer alloy (a) were measured. The average value of the dispersed diameters of the island components composed of the high color-developing polyester (B) was taken as the dispersion diameter of the island components composed of the high color-developing polyester (B) in the polymer alloy (a).

Regarding the island component discontinuity, 5 micrographs of the fiber cross section are taken at arbitrary intervals of at least 10000 times the single yarn diameter within the same single yarn, and the number of island components in each fiber cross section is counted. When the shape of the sea-island structure was different, the island component was regarded as discontinuous.

I. Specific Gravity The specific gravity was calculated using the fiber obtained in the example as a sample and according to the float-and-sink method of JIS L1013:1999 (chemical fiber filament yarn test method) 8.17. Water was used as the heavy liquid, and ethyl alcohol was used as the light liquid to prepare a specific gravity measurement solution. About 0.1 g of the sample was allowed to stand in the specific gravity measuring liquid for 30 minutes in a constant temperature bath at a temperature of 20±0.1° C., and then the state of floating and sinking of the sample was observed. A heavy liquid or a light liquid was added according to the floating and sinking state, and after standing for an additional 30 minutes, the sample was confirmed to be in a floating and sinking equilibrium state, 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 taken as the specific gravity.

J. Operability in Higher-order Processing Using the fiber obtained in the example as a sample, FR (feed roller), 1DR (1 draw roller), heater, cooling plate, false twisting device, 2DR (2 draw rollers), 3DR (3 A draw roller), an entangling nozzle, 4DR (4 draw rollers), and a winder were used for false twisting for 10 hours to obtain a false twisted yarn. The conditions for draw false twisting are as follows.

FR speed: 350 m/min, processing ratio between FR and 1DR: 1.05 times, hot plate type contact heater (length 110 mm): 145°C, cooling plate length: 65 mm, friction disk type friction texturing device, 2DR-3DR magnification: 1.0 times, 3DR-4DR magnification: 0.98 times, 4DR-winder magnification: 0.94 times.

After false twisting, observe the various rollers, friction disk type friction false twisting device, and guide. , and "excessive amount of sediments" were evaluated as x, and ◯ and ⊚ were evaluated as acceptable.

K. Uniform dyeing property Using the fiber obtained in the example as a sample, about 2 g of tubular knitting was produced using a circular knitting machine NCR-BL manufactured by Eiko Sangyo Co., Ltd. (bottle diameter 3 and a half inches (8.9 cm), 27 gauge), After scouring at 80°C for 20 minutes in an aqueous solution containing 1.5 g/L of sodium carbonate and 0.5 g/L of the surfactant Granup US-20 manufactured by Meisei Chemical Industry Co., Ltd., it is washed with running water for 30 minutes and dried with hot air at 60°C. Dried in the machine for 60 minutes. The tubular knit after scouring is dry heat set at 125 ° C. for 1 minute, and 1.3% by weight of Kayalon Polyester Blue UT-YA manufactured by Nippon Kayaku is added as a disperse dye to the tubular knit after dry heat setting, and the pH is adjusted. After dyeing at 130° C. for 45 minutes at a bath ratio of 1:100 in a dyeing solution adjusted to 5.0, the fabric was washed with running water for 30 minutes and dried in a hot air dryer at 60° C. for 60 minutes. The tubular knit after dyeing is soaked in an aqueous solution containing 2 g/L of sodium hydroxide, 2 g/L of sodium dithionite, and 0.5 g/L of Meisei Chemical Industry's surfactant Granup US-20 in a bath ratio of 1:100. After reduction 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 washing, the tubular knitting was dry-heat set at 125° C. for 1 minute to perform finish setting. Tubular knitting after finish setting was evaluated by 4 grades of ⊚, ∘, Δ, and × by discussion among 5 inspectors who have more than 5 years of experience in determining uniform dyeability. Evaluation shows that ⊚ is the best, ∘ and Δ are worse in order, and × is the worst. ◎ for “very evenly dyed, no uneven dyeing”, ○ for “almost uniformly dyed, almost no uneven dyeing”, “almost not evenly dyed” , faint dyeing spots are observed”, △ is “not uniformly dyed, and dyeing spots are clearly observed”, and “almost uniformly dyed, almost no dyeing spots are observed”. ○ or more was considered to have passed.

L. Color Development The tubular knitting produced in K above after finish setting was evaluated by a panel of 5 inspectors who have more than 5 years of color development experience, and was evaluated on a scale of ⊚, ○, Δ, and ×. Evaluation shows that ⊚ is the best, ∘ and Δ are worse in order, and × is the worst. ◎ for “sufficient vivid and deep color development and extremely excellent color development”, ○ for “generally sufficient vivid and deep color development and excellent color development”, “vivid and deep color development” Almost no, poor color development” is △, “no vivid and deep color development, extremely poor color development” is x, and “bright and deep color development is generally sufficient, excellent color development” ○ or more was defined as a pass.

Example 1
Polypropylene (PP) (Taiwan Plastics Co., Ltd. 1352F, melting peak temperature 165 ° C., MFR 35 g / 10 minutes) at a blending ratio of 80% by weight and 20% by weight of polyethylene terephthalate copolymerized with 20 mol% of cyclohexanedicarboxylic acid. Kneading was performed at a kneading temperature of 230° C. using a Ruder. After the strand discharged from the twin-screw extruder was water-cooled, it was cut into lengths of about 5 mm by a pelletizer to obtain pellets. The obtained pellets are used as a core component, dried in a vacuum at 95° C. for 12 hours, then supplied to an extruder-type melt spinning machine at a compounding ratio of 80% by weight and melted, and polypropylene (PP) is used as a sheath component, 20% by weight. % compounding ratio to an extruder-type melt spinning machine separate from the core component and melted, and a core-sheath type composite spinneret (1 island, discharge hole diameter 0.18 mm, discharge hole length 0.23 mm, number of holes 36, round holes) to obtain a spun yarn. The spun yarn is cooled with cooling air at a temperature of 20° C. and a speed of 25 m/min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m/min. The yarn was passed through a second godet roller rotating at the same speed as the dead roller and wound up with a winder to obtain an undrawn yarn of 105 dtex-36 f. The obtained undrawn yarn was drawn under conditions of a first hot roller temperature of 20° 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-36 f.

Table 1 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. The fiber surface is covered with polypropylene with a low refractive index, and the core component is a polymer alloy in which copolymerized polyethylene terephthalate with a low refractive index and high color development is finely dispersed in the polypropylene with a low refractive index. A certain color development was obtained, and both the color development and the workability in higher processing were acceptable levels. Furthermore, the entire fabric was uniformly dyed, and uniform dyeability was also good.

Examples 2-8
In Examples 2 to 6, drawn yarns were produced in the same manner as in Example 1, except that the copolymerization ratio of cyclohexanedicarboxylic acid was changed as shown in Table 1. In Examples 7 and 8, drawn yarns were produced in the same manner as in Example 1, except that the copolymerization components of polyethylene terephthalate were changed to isophthalic acid and adipic acid, and the copolymerization ratio was changed as shown in Table 1.

Table 1 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. As the copolymerization rate of cyclohexanedicarboxylic acid increased, the refractive index decreased and the color developability improved. In Examples 7 and 8, instead of cyclohexanedicarboxylic acid, isophthalic acid and adipic acid were used for copolymerization to reduce the refractive index. Both operability in processing was at an acceptable level. Furthermore, the entire fabric was uniformly dyed, and uniform dyeability was also good.

Comparative example 1
A drawn yarn was produced in the same manner as in Example 1, except that the polyester was changed to polyethylene terephthalate (PET) (T701T manufactured by Toray Industries, melting point: 257°C).

Table 2 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. Although the polyethylene terephthalate in the core component is dyed with a dye, due to the high crystallinity of the polyethylene terephthalate, the dye is insufficiently absorbed, and vivid and deep color development cannot be obtained, resulting in insufficient color development. Met. Further, the fineness fluctuation value U% (hi) was high and the uniformity in the longitudinal direction of the fiber was insufficient, resulting in poor uniform dyeability.

Comparative example 2
Polypropylene is supplied to an extruder-type melt spinning machine and melted, and a spinneret (discharge hole diameter 0.18 mm, discharge hole length 0.23 mm, number of holes 36, round hole ) to prepare a drawn yarn in the same manner as in Example 1, except that the spun yarn was obtained.

Table 2 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. It is a single PP yarn and has excellent runnability in high-order processing, but insufficient color development.

Comparative example 3
Polyethylene terephthalate obtained by copolymerizing 80% by weight of polypropylene and 40 mol% of 1,4-cyclohexanedicarboxylic acid was mixed at a blending ratio of 20% by weight at a kneading temperature of 230° C. using a twin-screw extruder. After the strand discharged from the twin-screw extruder was water-cooled, it was cut into lengths of about 5 mm by a pelletizer to obtain pellets. The obtained pellets were vacuum-dried at 95° C. for 12 hours, supplied to an extruder-type melt spinning machine, melted, and spun at a spinning temperature of 240° C. and a discharge rate of 31.5 g/min. A drawn yarn was produced in the same manner as in Example 1, except that the spun yarn was obtained by discharging from a circular hole having a discharge hole length of 0.23 mm and a number of holes of 36.

Table 2 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. Since amorphous copolymerized polyethylene terephthalate was exposed on the surface of the fiber, white powder was generated during operation in high-order processing, and the workability in high-order processing was extremely poor. In addition, vivid and deep color development was obtained, and the color development was at an acceptable level.

Examples 9-23
In Examples 9 to 13, amine-modified styrene-ethylene-butylene-styrene copolymer (JSR Dynaron 8660P) was used as a compatibilizer, and the composite ratio of polypropylene, cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate, and compatibilizer is shown. A drawn yarn was produced in the same manner as in Example 2, except that it was as shown in 2. In Examples 14 to 19, the compatibilizer was an amine-modified styrene-butadiene-butylene-styrene copolymer, or an amine-modified styrene-ethylene-butylene-styrene copolymer and an amine-modified styrene-butadiene-butylene-styrene copolymer. Drawn yarn was prepared in the same manner as in Example 2, except that a mixture obtained by mixing at a weight ratio of 1:1 was used, and the composite ratio of polypropylene, cyclohexanedicarboxylic acid copolymerized polyethylene terephthalate, and compatibilizer was set as shown in Table 2. made. In Example 20, imine-modified styrene-ethylene-butylene-styrene copolymer was used, and the composite ratio of polypropylene, cyclohexanedicarboxylic acid-copolymerized polyethylene terephthalate, and compatibilizing agent was as shown in Table 2. A drawn yarn was prepared in the same manner as. In Examples 21 to 23, amine-modified styrene-ethylene-butylene-styrene copolymer (Dynaron 8660P manufactured by JSR) was used as a compatibilizer, and the composite ratio of polypropylene, isophthalic acid/adipic acid copolymer polyethylene terephthalate, and compatibilizer was A drawn yarn was produced in the same manner as in Example 8, except that the was set as shown in Tables 2 to 4.

Tables 2 to 4 show the evaluation results of fiber properties and fabric properties of the obtained fibers. By using a compatibilizing agent, the dispersion diameter of the island component was reduced due to the compatibilizing effect, and vivid and deep coloring could be obtained. Further, due to the compatibilization effect, the fineness fluctuation value U % (hi) was low and the uniformity in the longitudinal direction of the fiber was good, so that the uniform dyeability was also extremely excellent.

Examples 24, 25
In Example 24, the polypropylene was changed to polymethylpentene (PMP) (Mitsui Chemicals DX820, melting point 232 ° C., MFR 180 g / 10 minutes), the kneading temperature was changed to 260 ° C., and the spinning temperature was changed to 260 ° C. A drawn yarn was produced in the same manner as in Example 9. In Example 25, a drawn yarn was produced in the same manner as in Example 21 except that polypropylene was changed to polymethylpentene, the kneading temperature was changed to 260°C, and the spinning temperature was changed to 260°C.

Table 4 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. Even when polymethylpentene was used as the polyolefin, vivid and deep color development was obtained, and both color development and workability in higher processing were good. In addition, the light weight and uniform dyeability were also at acceptable levels.

Examples 26-33
In Examples 26 to 30, drawn yarns were produced in the same manner as in Example 9, except that the core-sheath composite ratio was as shown in Table 5. In Examples 31 to 33, drawn yarns were produced in the same manner as in Example 21, except that the core-sheath composite ratio was as shown in Table 3.

Table 5 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. Even when the core-sheath composite ratio was changed, vivid and deep coloring could be obtained, and both the coloring property and the workability in higher processing were acceptable levels. Furthermore, the entire fabric was uniformly dyed, and uniform dyeability was also good.

Examples 34, 35
Example 34 was the same as Example 9, except that the spinneret was changed to a sea-island composite spinneret (6 islands, discharge hole diameter 0.18 mm, discharge hole length 0.23 mm, number of holes 36, round holes). A drawn yarn was produced. Example 35 was the same as Example 21, except that the spinneret was changed to a sea-island composite spinneret (6 islands, discharge hole diameter 0.18 mm, discharge hole length 0.23 mm, 36 holes, round holes). A drawn yarn was produced.

Table 4 shows the evaluation results of the fiber properties and fabric properties of the obtained fibers. Bright and deep color development was obtained regardless of the cross section of the fiber, and both the color development and the workability in higher processing were acceptable levels. Furthermore, the entire fabric was uniformly dyed, and the uniform dyeability was extremely good.

INDUSTRIAL APPLICABILITY The dyeable polyolefin fiber of the present invention is obtained by imparting bright and deep color development to the polyolefin fiber which is excellent in light weight, and can be suitably used as a fiber structure.

Claims (7)

The sheath component is a polyolefin (A), the core component is a polymer alloy (a) composed of a polyolefin (A') and a highly colored polyester (B), and the highly colored polyester (B) is a constituent component of two or more dicarboxylic acids. and a dyeable polyolefin core-sheath type composite fiber which is a copolymer polyester having a refractive index of 1.40 to 1.58 . 2. The dyeable polyolefin core-sheath type composite fiber according to claim 1, wherein the polymer alloy (a) contains a compatibilizer (C). A styrene-ethylene-butylene-styrene copolymer and/or a styrene-butadiene-butylene-styrene copolymer in which the compatibilizer (C) contains at least one functional group selected from an amino group and an imino group The dyeable polyolefin core-sheath type conjugate fiber according to claim 2 , characterized in that: The dyeable polyolefin core-sheath type composite according to any one of claims 1 to 3 , wherein the shortest distance from the fiber surface to the highly colored polyester (B) component is 0.1 to 5.0 μm. fiber. 5. The polymer alloy (a) according to any one of claims 1 to 4 , wherein the mass ratio of the polyolefin (A') to the highly colored polyester (B) is 97/3 to 60/40. dyeable polyolefin core-sheath type composite fiber. A false-twisted yarn obtained by twisting two or more of the dyeable polyolefin core-sheath type conjugate fibers according to any one of claims 1 to 5 . A fiber structure characterized by using the dyeable polyolefin core-sheath type conjugate fiber according to any one of claims 1 to 5 and/or the false twisted yarn according to claim 6 at least in part.