JP4367117B2 - Hollow blend fiber with excellent light weight - Google Patents

Description

  The present invention relates to a hollow blend fiber excellent in lightness. More specifically, the present invention relates to a hollow blend fiber that is very excellent in fiber physical properties such as strength, lightness, and light shielding properties.

In recent years, technical development of synthetic fibers has made remarkable development, have been developed fiber with a variety of new features, the development of fiber that claim a "lightweight" Among them is, of lightweight clothing associated with high aging population It is attracting attention in terms of expansion, the popularity of outdoor sports and the expansion of lightweight or warm clothing, and the reduction of vehicle interior materials due to energy savings.

  For example, a blended composite fiber in which polyolefin is added to polyamide has been proposed (see Patent Document 1). In the composite fiber, the ratio of the polyolefin having a light specific gravity in the blended composite fiber is added in an amount of 1 to 50% by mass, and the mass fraction with the polyamide having a specific gravity of 1.13 is controlled, so that the apparent specific gravity of the composite fiber is 1. Although it is a fiber that is excellent in lightness by setting it to 03 to 1.13, the technique is mainly used for fishing fishing lines, and the fiber specific gravity is permanently maintained in a specific range of 1.03 to 1.13. Therefore, the interface between the polyolefin and the polyamide was a fiber that was not peeled off.

  Moreover, the porous hollow fiber which consists of a thermoplastic polymer is proposed (refer patent document 2). The hollow fiber is obtained by leaching the core component from the composite fiber in which a water-soluble polymer is disposed in the core component, and is certainly excellent in light weight, but in order to further improve the light weight, that is, to further reduce the specific gravity. Since it is necessary to increase the number of hollow parts, the design of the polymer discharge holes, the core-sheath composite spinning conditions, and the arrangement of the core-sheath (or sea island) in the raw yarn have become complicated and technically versatile. As a result, there was a limit to the improvement in lightness.

A lightweight polyester fiber composed of a polyester resin and a styrene / maleimide resin having a molecular weight of 60 to 170,000 has been proposed (see Patent Document 3). The lightweight polyester fiber is a fiber having a large number of fine cavities due to the separation of the polyester resin and the styrene / maleimide resin, but the polymer having a maleimide structure originally tends to have a yellowish color and is used for clothing. The application was limited to the application, and the difference in critical surface tension between the styrene / maleimide resin and the polyester resin is less than 10 dyne / cm, the adhesion between the resins is good, and the fine cavity for weight reduction. Therefore, a very high drawing tension was required for the development of yarn, and as a result, yarn breakage in the drawing process was likely to occur, resulting in poor operability and yarn properties. Further, in producing the lightweight polyester fiber, it is said that the fine cavities are expressed when the drawing is performed, but specific technical guidelines regarding the drawing for developing the cavities are not shown, and are described in Examples. The expression of the fine cavities cannot be achieved only by the method of setting the roller of the stretching machine used to 85 ° C.
JP-A 63-296641 JP 2002-173831 A (claim, paragraph [0004]) JP 2000-154427 A (claims, paragraph [0012])

  An object of the present invention is to provide a hollow blend fiber that solves the above-mentioned problems of the prior art, is extremely excellent in lightness, and has excellent fiber physical properties such as strength or light shielding properties.

  The present invention relates to a fiber having excellent lightness, and has been intensively studied to obtain a hollow blend fiber having excellent fiber physical properties such as strength and light shielding properties, which is useful for various clothing materials or industrial materials. It has been found that a specific fiber structure and physical properties containing a specific substance can eliminate the disadvantages of the prior art and can provide further advantages that cannot be achieved with the prior art. The invention has been reached.

That is, according to the present invention, in the blended fiber composed of the component A having fiber forming ability and the component B which is a thermoplastic polymer, the relationship between the critical surface tension γ _cA of the component A and the critical surface tension γ _cB of the component B is γ _cA −. γ _cB ≧ 10 dyne / cm, the glass transition temperature (Tgb) of component B is 5 ° C. or higher and 130 ° C. or higher than the glass transition temperature (Tga) of component A, and component A The hollow having excellent light weight, characterized in that the component B forms an island, and further has a void in at least a part of the composite interface between the component A and the component B, and has a hollow portion communicating in the fiber axis direction. A blended fiber is provided.

The hollow blended fiber obtained by the present invention has a hollow portion in the fiber that communicates with the gap in the fiber axis direction, and thus is very preferable because it is excellent in light weight and light shielding properties. In addition, in terms of fiber properties, the fiber strength can be 3.5 cN / dtex or more, or the apparent specific gravity of the fiber can be 1.2 or less. As a textile product, uniform clothing such as lab coats, underwear, T-shirts, In addition to shirts, swimwear, women's clothing, men's clothing, etc., as well as lightweight clothing for infants or the elderly, sports clothing such as golf wear, gateball, baseball, tennis, soccer, table tennis, volleyball, basketball , Rugby, American football, hockey, athletics, triathlon, speed skating, ice hockey and other clothing and uniforms, or outdoor sports applications such as shoes, bags, supporters, socks and climbing trees. Furthermore, as industrial materials, car interior materials such as carpets and wall materials for automobiles, ships, airplanes, railways, etc. that are particularly required to be lightened due to energy saving, as well as ropes, tents, curtains, blinds, or various types It is also suitably used for materials that require lightness and light shielding properties such as packing materials used for transportation.

Component A forming the hollow blend fiber of the present invention has fiber forming ability. The fiber in the present invention refers to a thin and long shape and may be a long fiber (filament) or a short fiber (staple) generally referred to, or a very short, usually used for electric flocking, etc. may be a fiber length of less than 10 mm, Ru recognized as having a fiber forming ability as long as the polymer which can without these fiber form.

  Component A forming the hollow blend fiber used in the present invention is a polymer having fiber-forming ability, and examples of polymers used for general purposes include polyester-based polymers, polyamide-based polymers, polyimide-based polymers, and polyolefin-based polymers. Examples thereof include polyvinyl polymers, fluorine polymers, cellulose polymers, silicone polymers, elastomers, and various other engineering plastics formed by polymerization of polymers and other vinyl groups.

  More specifically, for example, as a polyolefin polymer synthesized by a mechanism in which a monomer having a vinyl group is generated by an addition polymerization reaction such as radical polymerization, anion polymerization, and cationic polymerization, and other polyvinyl polymers, , Polyethylene, polypropylene, polybutylene, polymethylpentene, polystyrene, polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, vinylidene polycyanide, etc. However, these may be polymers obtained by homopolymerization, such as polyethylene alone or polypropylene alone, or copolymer polymers formed by conducting a polymerization reaction in the presence of a plurality of monomers. Is good, for example, styrene and Doing polymerization in methyl methacrylate presence poly - but polymers copolymerized as (styrene methacrylate) is produced, it may be a polymer which is such a copolymer.

  Examples of component A include polyamide polymers formed by the reaction of carboxylic acids or carboxylic acid chlorides with amines. Specifically, nylon 6, nylon 7, nylon 9, nylon 11, nylon 12 can be mentioned. Nylon 6,6, Nylon 4,6, Nylon 6,9, Nylon 6,12, Nylon 5,7, Nylon 5,6 and the like, and other aromatics within a range not impairing the gist of the present invention, Aminocarboxylic acid in which aliphatic, alicyclic dicarboxylic acid and aromatic, aliphatic, alicyclic diamine component, or one compound such as aromatic, aliphatic, alicyclic has both carboxylic acid and amino group The compound may be used alone, or may be a polyamide polymer in which the third and fourth copolymer components are copolymerized.

Examples of component A include a polyester polymer formed by an esterification reaction of a carboxylic acid and an alcohol. Specifically, examples of the polyester-based polymer used in the present invention include a polymer formed from an ester bond of a dicarboxylic acid compound and a diol compound. Examples of such a polymer include polyethylene terephthalate and polypropylene terephthalate. , Polybutylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate. The polyester polymer formed from the ester bond of the dicarboxylic acid compound and the diol compound may be copolymerized with other components as long as the gist of the present invention is not impaired. For example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylethanedicarboxylic acid, adipic acid, sebacic acid, 1,4 -Aromatic, aliphatic, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, azelaic acid, dodecanedioic acid, hexahydroterephthalic acid And derivatives, adducts, structural isomers and optical isomers such as alkyl, alkoxy, allyl, aryl, amino, imino and halides, and one of these dicarboxylic acid compounds can be used alone. Alternatively, two or more kinds may be used in combination as long as the gist of the invention is not impaired.

  Examples of the copolymer component include diol compounds such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, hydroquinone, resorcin, dihydroxybiphenyl, naphthalenediol, anthracene. Aromatic, aliphatic and alicyclic diol compounds such as diol, phenanthrenediol, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, bisphenol S, and their alkyl, alkoxy, allyl, Derivatives, adducts, structural isomers, and optical isomers such as aryl, amino, imino, and halide can be listed. One of these diol compounds can be used alone. May be used, or in a range that does not impair the gist of the invention may be used in combinations or two or more kinds.

  Examples of the copolymer component include a compound having a hydroxyl group and a carboxylic acid in one compound, that is, a hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include lactic acid, 3-hydroxypropionate, and 3-hydroxybutyrate. Aromatic, aliphatic and alicyclic diol compounds such as acrylate, 3-hydroxybutyrate valerate, hydroxybenzoic acid, hydroxynaphthoic acid, hydroxyanthracenecarboxylic acid, hydroxyphenanthrenecarboxylic acid, (hydroxyphenyl) vinylcarboxylic acid, and their Derivatives, adducts, structural isomers and optical isomers such as alkyl, alkoxy, allyl, aryl, amino, imino, and halide can be mentioned, and one of these hydroxycarboxylic acids may be used alone. Or It may be used in combination of two or more in a range that does not impair the Ming gist.

As the polyester-based polymer, an aromatic, aliphatic, it may be a polymer in which one compound is a hydroxycarboxylic acid compound having both a carboxylic acid and a hydroxyl group as the main repeating unit of an alicyclic, for example those Examples of the polymer include poly (hydroxycarboxylic acid) such as polylactic acid, poly (3-hydroxypropionate), poly (3-hydroxybutyrate), and poly (3-hydroxybutyrate valerate). In addition, these poly (hydroxycarboxylic acids) can be aromatic, aliphatic, alicyclic dicarboxylic acids, or aromatic, aliphatic, alicyclic diol components within the range not detracting from the gist of the present invention. May be used, or a plurality of hydroxycarboxylic acids may be copolymerized.

  In addition, the polymer of component A having fiber-forming ability used in the present invention is formed by a polycarbonate polymer formed by a transesterification reaction between an alcohol and a carbonic acid derivative, or a cyclized polycondensation of a carboxylic acid anhydride and a diamine. Polyimide polymers, polybenzimidazole polymers formed by the reaction of dicarboxylic acid esters and diamines, as well as polysulfone polymers, polyether polymers, polyphenylene sulfide polymers, polyether ether ketone polymers, polyether ketone ketone In addition to synthetic polymers such as polymer polymers, cellulose polymers and polymers derived from natural polymers such as chitin, chitosan, and derivatives thereof are also included. As will be described later, since the component A and the component B form a preferable blended state in a molten state, among the polymers mentioned as the component A, a polymer having thermoplasticity is preferable.

  Among these polymers having fiber-forming ability, component A has a very large glass transition temperature difference (Tgb-Tga) as described later, so that a large gap is formed at the interface between component A and component B. Polyolefin polymers are preferred because they are easy to produce, or are excellent in spinnability or stretchability during fiber formation. Among these polyolefin polymers, a polyolefin polymer having no side chain or having a small side chain length, such as polyethylene, polypropylene, or polybutylene, is more preferable because it can be designed to have a large glass transition temperature difference from Component B. The glass transition temperature Tg referred to here is B.B. It is measured by the method.

Similarly, among these polymers having fiber-forming ability, component A has a large critical surface tension γ _cA and a low tension during stretching as described later, and voids appear at the interface with component B during stretching. From the standpoint of ease of treatment, component A is preferably a polyester-based polymer or a polyamide-based polymer, and a polyester-based polymer is more preferable because it can improve lightness during stretching. Of these polyester polymers, a polyester polymer in which the main repeating unit is ethylene terephthalate, propylene terephthalate, butylene terephthalate, or lactic acid is preferable, and since the melting point is high and heat resistance is excellent, the polyester system in which the main repeating unit is ethylene terephthalate. A polymer is more preferred. Polyamide polymers such as nylon 6 and polyester polymers such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are described later in C.I. In both methods, the copolymer has a critical surface tension γ _cA of about 43 dyne / cm, but a copolymerized component such as sulfoisophthalate or phosphate that can increase the critical surface tension. Is preferable because a critical surface tension γ _c larger than 43 dyne / cm can be obtained.

Regarding the critical surface tension γ _cA of the component A of the present invention, the relationship between the critical surface tensions of the component A and the component B, which will be described later, is that the interfacial peeling between the component A and the component B is more efficiently expressed. Since a larger value of γ _cA −γ _cB is preferable for interfacial peeling, the value of γ _cA is preferably 35 dyne / cm or more, more preferably 38 dyne / cm or more, and 40 dyne / cm or more. Particularly preferred.

The viscosity of the polyester polymer are preferred as component A of the present invention, (sometimes hereinafter referred to as IV) intrinsic viscosity to be subjected to ordinary synthetic fiber polyester polymer to be used for. For example, if it is a polyethylene terephthalate, it is preferable that IV is 0.4-1.5, and it is more preferable that it is 0.5-1.3. Moreover, if it is a polypropylene terephthalate, it is preferable that IV is 0.7-2.0, and it is more preferable that it is 0.8-1.8. Or if it is polybutylene terephthalate, it is preferable that IV is 0.6-1.5, and it is more preferable that it is 0.7-1.4. Examples of polyesters used in the present invention whose viscosity is not evaluated by IV include, for example, polylactic acid, but these are not IV but weight average molecular weight (hereinafter sometimes simply referred to as average molecular weight). For example, polylactic acid having an average molecular weight of 50,000 to 500,000 is usually used, preferably 100,000 to 300,000, and 150,000 to 250,000 in view of processability and spinnability. Polylactic acid having an average molecular weight of 2 is more preferably used. In the polyamide polymer, intrinsic viscosity [η] is used. For example, in the case of nylon 6, [η] is preferably 1.9 to 3.0, and 2.1 to 2.8. More preferred.

  Component A may be a single polymer selected from these, or a plurality of types may be used in combination as long as the gist of the invention is not impaired.

Content of the component A in the hollow blend fiber of this invention is 50 weight% or more , and can take arbitrary content. In particular, since component A influences fiber physical properties in fiber physical properties and is preferable for ensuring stable fiber physical properties, the content of component A in the hollow blend fiber is preferably 70 to 99.5% by weight, More preferably, it is 80-98 weight%, More preferably, it is 85-95 weight%.

  Component B, which is the thermoplastic polymer of the present invention, forms a blended fiber with Component A as will be described later, and forms islands in the cross section of the single fiber, that is, substantially non-phasic with respect to Component A. It is melted. In the present invention, “incompatible” means that the component A and the component B are not compatible with each other in the molecular chain size order of the polymer, and the average domain size formed by the component B in the component A (the shortest diameter in the domain). (Corresponding length) having a size of at least 10 nm. It is confirmed by the method. When component A and component B are compatible, that is, when the average domain size formed by component B is less than 10 nm, component B forms a blended fiber with component A, but the island formed by component B described above Is a very small domain, does not have voids, or does not sufficiently exhibit voids necessary for a fiber having excellent lightness, resulting in a hollow blend fiber having poor lightness.

Component B of the present invention is a non-compatible as described above with respect to component A, which constitutes the islands if the no blended fibers, similar to the component A wide variety of thermoplastic polymers, component It can be used in consideration of the incompatibility between A and component B. For example, a polyester polymer, a polyamide polymer, a polyimide polymer, a polyolefin polymer, other vinyl polymers, a fluorine polymer, a cellulose polymer, a silicone polymer, an elastomer, and various other engineering plastics can be used.

  More specifically, when a polyester-based polymer or a polyamide-based polymer is adopted as the component A that is preferable as described above, it is preferable from the viewpoint of critical surface tension, density, or glass transition temperature (Tg) described later. As component B, mention may first be made of polyolefin polymers. As described above, the polyolefin-based polymer is an aromatic, aliphatic, or alicyclic monomer having a vinyl group, such as radical polymerization, anionic polymerization, or cationic polymerization, by addition polymerization reaction or ring-opening polymerization reaction. A generic term for polymers such as polyolefins and other vinyl polymers synthesized by the mechanism by which the polymer is formed. For polyolefins, for example, homopolymers, copolymers, and derivatives of polyethylene, polypropylene, polybutylene, and polymethylpentene are used. Other vinyl polymers include polystyrene, polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polyvinylidene chloride, polynorbornyl Such emissions and copolymers and derivatives thereof.

  Among those exemplified as the polyolefin-based polymer, preferable component B includes polyolefins such as ethylene, propylene, butene, methylbutene, methylpentene, ethylpentene, hexene, ethylhexene, octene, decene, tetradecene, and octadecene. In addition to the polyolefin using as a monomer, for example, a polyolefin polymer having a cyclic structure represented by the following chemical formula 1, chemical formula 2, or chemical formula 3, which is synthesized by ring-opening polymerization or addition polymerization of an alicyclic monomer. It is done.

Here, each of the substituents X and Y is a group selected from hydrogen, an alkyl group, an alicyclic group, a cyano group, an alkyl ester group, and an alicyclic ester group.

As those having the structure, for example, JSR Co., ARTON (registered trademark), Nippon Zeon's Zeonoa (registered trademark) is Ru mentioned.

These polyolefin polymers may be homopolymers using one kind of monomer alone, or may be a copolymer using two or more kinds, and further copolymerize olefins with other vinyl compounds. It may be a copolymer. Specific examples of the copolymer component include vinyl esters of saturated aliphatic carboxylic acids having 2 to 6 carbon atoms, acrylic acid esters and methacrylic acid esters derived from alcohols having 1 to 20 carbon atoms, Unsaturated carboxylic acids such as fumaric acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid, acid halides, amides, imides, acid anhydrides and esters of the unsaturated carboxylic acids, Examples thereof include vinyl compounds such as styrene or styrene derivatives, acrylonitrile or acrylonitrile derivatives, vinyloxyalkyl derivatives (alcohol type or carboxylic acid type), or vinyl compounds having an alicyclic structure. Particularly polyolefin polymer having the alicyclic structure as a copolymer component, for example, by Mitsui Chemicals Co. APEL (registered trademark) is Ru mentioned.

  Among the polyolefin polymers exemplified as preferable in these components B, the polyolefin polymer having propylene and / or methylpentene as a main repeating unit or a cyclic structure is used in that the void formation property of the formed fiber is high. A polyolefin polymer and a copolymer polyolefin polymer having an alicyclic structure are preferred.

As the component B of the present invention, as described above, when the component A is preferably a polyester polymer, polyamide polymer, or polyolefin polymer, a polyether polymer is also included, among which polyphenylene ether Aromatic polyether polymers represented by the above are preferred. The aromatic polyether polymer may be a homopolymer mainly composed of phenylene oxide or a copolymer obtained by copolymerizing the second component, and does not impair the gist of the invention. The modified polyphenylene ether may be an alloy containing as a second component an additive-containing material, that is, a polystyrene polymer, a polyamide polymer, a polyester polymer, a polyolefin polymer, or the like. Examples of the modified polyphenylene ether include Iupiace (registered trademark) and Remalloy (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., Noryl (registered trademark) manufactured by GE Plastics Co., Ltd., and Asahi Kasei Co., Ltd. of Zylon (registered trademark), manufactured by Sumitomo chemical Co., Ltd. of Art Rex (registered trademark), Art Lee (registered trademark) Ru is like. The aromatic polyether polymer is preferable in that Tg is usually 150 ° C. or higher and the glass transition temperature is high as described later in the present invention.

Component B in the present invention can be used in combination with Component A within a range that does not detract from the gist of the present invention. However, when the hollow blend fiber of the present invention is used, the use of the component B is expected. Limited and may not be preferred. Therefore, in order to avoid coloring due to the yellowing, it may be preferable that the molecular skeleton of Component B does not have a maleimide structure. When the component B has the maleimide structure, as described above, not only may there be a demerit that the fiber after generation is yellowed, but depending on the combination with the component A, the affinity between the component A and the component B Since the property is too high, the void formation is poor, and sufficient lightness may not be exhibited. Alternatively, the light shielding property of the fiber obtained by inferior void formation may be low. Examples of the component B having a maleimide structure include a styrene maleimide polymer (type: MS-NA, etc.) manufactured by Electrochemical Co., Ltd. In the case where it is not necessary, the component B having a maleimide structure may be used at all.

  As the component B in the present invention, one kind of various polymers exemplified above may be used alone, or a plurality of kinds may be used in combination as long as the gist of the invention is not impaired.

The component B used in the present invention is more suitable as the density is smaller in that the fiber feels lighter, and the density is preferably 1.0 g / cm ³ or less. In the previous mentioned component B, the include polyolefin-based polymers, among them, as said seal degree of 1.0 g / cm ³ or less, ethylene and / or propylene and / or butylene and / or methylpentene More preferably, a homopolymer or copolymer of polyolefin in which 80 mol% or more occupies 80 mol% or more, and even more preferably a homopolymer or copolymer in which propylene and / or methylpentene occupy 80 mol% or more. In particular, in the copolymer according propylene and / or methyl pentene account for at least 80 mol%, those which are copolymerized in order to improve the workability such as stretchability and plasticity, for example, carbon atoms 5 Examples include those obtained by copolymerizing the above aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, or vinyl compounds having derivatives thereof in the side chain. The density is more preferably 0.95 g / cm ³ or less, and even more preferably 0.90 g / cm ³ or less.

The average molecular weight of the component B used in the present invention also preferably has a number average molecular weight in terms of shape retention and rigidity is 2,000～10,000,000 during fibers, 5,000～5, More preferably, it is 1,000,000, and even more preferably 10,000 to 1,000,000.

The melt viscosity of the component B used in the present invention is a melt spinning temperature of the polyester used, shear rate shear viscosity of 10 sec ^-1 is used usually polymers 10-100,000 poise, preferably 100 to 50,000 It is a poise.

In the hollow blend fiber of the present invention, the component B has a glass transition temperature (Tgb) of the component A in that voids are easily generated when the hollow blend fiber is stretched and the resulting fiber is lighter. It is preferably 5 ° C. or more higher than the transition temperature (Tga). Here, the glass transition temperature (Tg) refers to B. of Examples described later. It is defined by the method. Tgb is more preferably 10 ° C. or higher than Tga, more preferably 30 ° C. or higher, and particularly preferably 50 ° C. or higher. When Tgb is higher than Tga by 5 ° C. or more, not only the interface peeling between component A and component B appears in the formation of voids during stretching, but also the cracking and peeling of component B itself. Furthermore, also in melt spinning, component B is preferable because it solidifies at a higher temperature than component A and forms a structure advantageous for void formation, and also improves lightness. The glass transition temperature of the component B constituting the island component (Tgb), in that is more suitable for void generation is 130 ° C. or higher. The glass transition temperature Tga of each component A is 72 ° C. for polyethylene terephthalate, 47 ° C. for polypropylene terephthalate, 24 ° C. for polybutylene terephthalate, 58 ° C. for polylactic acid, and polycyclohexane. In the case of dimethanol terephthalate, it is observed at 87 ° C., in the case of polyethylene naphthalate, at 122 ° C., and in the case of nylon 6, it is observed at 72 ° C. (however, when dried at 133 Pa or less for 12 hours or more).

The addition amount of the component B in the hollow blend fibers used in the present invention, those may be appropriately determined in accordance with the characteristics such as light weight, or spinnability a combination and the purpose of the components A and B employed, more The content of component B in the hollow blend fiber of the present invention is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, from the viewpoint that it is excellent in yarn-making property and can be imparted with moderate lightness. Even more preferred is 20% by weight.

  In the present invention, a polymer other than Component A and Component B can be blended with the blend polymer for spinning as long as the effects of the present invention are not hindered.

Relationship critical surface tension gamma _cB of the critical surface tension gamma _cA and component A to component B of the present invention, Ru γ _cA -γ _cB ≧ 10dyne / cm der. If the critical surface tension of the relationship gamma _{cA-gamma cB} is 10 dynes / cm or more, in the mechanism of the present invention that expression voids within After peeling during stretching at the interface of the component A and component B, the field surface is peeled off easy that light weight of the composite fiber is Re Yu. The relationship gamma _{cA-gamma cB} of the critical surface tension from the excellent light weight easily expressed voids as takes a large value, it is good Mashiku is 13dyne / cm or more, it is 15 dyne / cm or more good more preferable. The upper limit of the relationship γ _cA -γ _cB can be usually 50 dyne / cm or less from the combination relationship.

Examples of the combination of components A and B satisfy the relationship of the critical surface tension of _{γ cA -γ cB ≧ 10dyne / cm} , for example, a polyester-based polymer including polyethylene terephthalate or polypropylene terephthalate and component A, polyethylene and polypropylene , A combination in which a polyolefin polymer such as polymethylpentene is used as the component B, or a combination in which a polyamide polymer such as nylon 6 or nylon 66 is used as the component A and the aforementioned polyolefin polymer is used as the component B. A combination of polyethylene terephthalate or polypropylene terephthalate as component A and polymethylpentene as component B is more preferable.

In addition, the component B of the present invention peels off at the interface between the component A and the component B of the composite fiber obtained by the method of the present invention to easily express voids, and the resulting composite fiber is more lightweight. In this respect, the critical surface tension γ _cB of component B is preferably 10 to 30 dyne / cm, and more preferably 15 to 25 dyne / cm. Examples of the component B that satisfies this critical surface tension γ _cB range include, for example, a fluorine-based polymer (18 to 28 dyne / cm), a silicone-based polymer (18 to 25 dyne / cm), and a polyolefin-based polymer (24 to 30 dyne / cm). Among them, polyolefin polymers are more preferable from the viewpoint of the above-mentioned density, and among the polyolefins composed of the above-mentioned olefin monomers or other ethylenically unsaturated compounds, propylene and / or methylpentene is 80 mol%. The homopolymer or copolymer occupying the above is preferable, the homopolymer or copolymer occupying 80 mol% or more of methylpentene is more preferable, and the combination of the polyester as component A is extremely excellent in void development, preferable. In particular, in the case of a homopolymer or copolymer in which the above-mentioned propylene accounts for 80 mol% or more, 29 to 30 dyne / cm, and in the case of a homopolymer or copolymer in which methylpentene accounts for 80 mol% or more, 24 to 25 dyne / cm. cm.

In the components A and B of the present invention, the relationship between the melting point Tma of the component A and the melting point Tmb of the component B is preferably Tma> Tmb. When the relationship between the melting points satisfies Tma> Tmb, the component B is easily finely dispersed in the component A, and the void developability is preferable.

The component A used in the present invention, in that it avoids such heat resistance of the composite fibers obtained by the process of the present invention is good, that collapses the gap deformed component A at a high temperature, the melting point of component A Tma is preferably 160 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 250 ° C. or higher. Component B used in the present invention has good heat resistance of the hollow blended fiber, that is, even when the fiber obtained by the method of the present invention is exposed to high temperature, component B is deformed in the void to fill the void. The melting point Tmb of the component B is preferably 150 ° C. or higher, and more preferably 180 ° C. or higher in that it does not collapse, that is, it is excellent in lightness without crushing voids.

  The hollow blended fiber of the present invention is a blended fiber composed of main component A and component B. The blend fiber means a fiber formed from a blend composition in which component A and component B are kneaded (blended) at an arbitrary stage before melt spinning is completed by various methods as described below. In the part forming the fiber other than the hollow part of the single fiber cross section perpendicular to the fiber axis direction of the blended fiber, a sea island structure is formed in which the component A forms the sea and the component B forms two or more islands. And the component B which is an island exists discontinuously in the fiber axis direction (see FIG. 2). Here, it can be confirmed that the islands are discontinuously dispersed in the fiber axis direction by observing the cross section in the fiber axis direction by a measurement method to be described later. When a plurality of observations are performed in the fiber axis direction at an arbitrary interval of at least 1,000 times the diameter, it is assumed that the sea island structures having different cross-sections of the single fibers are discontinuous. Here, the discontinuity index indicates that the ratio β / α of the island diameter (α) (equivalent to a circle) and the length in the fiber axis direction (β) in the single fiber cross section is 1,000 or less. It is defined that the islands are discontinuously dispersed in the fiber axis direction, and β / α is preferably 100 or less, and more preferably 10 or less. And the blended fiber in the present invention is a core-sheath composite spinning in which one island is continuously formed in the same shape in the fiber axis direction, or a sea island in which a plurality of islands are formed in the same shape in the fiber axis direction. It is essentially different from composite spun fibers obtained from composite spinning. These composite spun fibers have a very small area at the blend interface as compared with the blend fiber of the present invention, and voids are not formed at the interface between the sea and the island, or almost no voids are formed and the lightness is poor. However, the hollow blended fiber made of the blended fiber of the present invention forms the sea with component A and the island with component B, so that the boundary between the sea and the island is separated by the example of the spinning method described below, and numerous voids are developed. Thus, the fiber is excellent in lightness.

The blending method of the component A and the component B for forming the hollow blend fiber of the present invention is , for example, (A) mixing the component A and the component B with chips or powders until the melt is discharged from the spinning discharge hole. A method of blending only the shear stress when the molten mixed polymer flows in the spinning channel, (B) Mixing component A and component B with chips or powder, and kneading machine such as an extruder or static mixer (C) Component B is added to Component A at a high concentration and blended under normal pressure or reduced pressure using a kneader such as an extruder or static mixer. After being obtained, in a kneader such as an extruder or a static mixer at the time of spinning, the master polymer and component A are mixed with the component B having a desired concentration. (D) In the usual polymerization reaction of component A, component B is added at an arbitrary stage before the polymerization reaction of component A stops. Method of blending, (E) After component A and component B are melted individually, the components A and B are metered together in the melted state in the pipe flow path, and only the shear stress when the molten mixed polymer flows Or a method of blending using a static mixer, and the like. However, since the blending can be easily achieved and the components A and B are kneaded more finely, the above-mentioned (B) and (C) are preferable. Alternatively, the method (E) is adopted.

In particular, regarding the extruder, a uniaxial or biaxial or more multiaxial extruder can be suitably used. However, when component A and component B are blended, component B is finely kneaded in component A. It is preferable to employ the above multi-axis extruder. The ratio 1 / w of the length (l) of the extruder shaft and the thickness (w) of the shaft is 1 / w in that the kneadability of the component A and the component B is further improved. Preferably, it is 20 or more, more preferably 30 or more. In particular, with regard to the static mixer, for example, the operation of dividing the flow path of the molten polymer into two or more and then reuniting (one operation from this division to the unification is performed as one stage) is performed. if the kneading element of that static standing, it is preferable that the number of stages of the static mixer is 5 or more stages in that more kneading property is excellent, it is still more preferably at least 10 stages. As for the installation location of the static mixer, if it is in the spinning machine, even before the device for measuring the discharge of the molten polymer, it is after the device for measuring until the discharge hole for the melt discharge. and not may be suitably used by installing, for example, a spinning pack having a melt discharge hole.

As described above, the average dispersion diameter of the island composed of component B in the hollow blend fiber of the present invention is such that the area of the blend interface between component A and component B is very large, and the voids present in at least part of the blend interface are fine. The average dispersion diameter is preferably from 0.01 to 5 μm because the average dispersion diameter is very large and the weight is extremely excellent. When the average dispersion diameter is 0.01 to 5 μm, the generated voids have an appropriate size and are unlikely to become a fiber defect, so that the fiber strength of the hollow blend fiber is not deteriorated and is very excellent. Are better. The average dispersion diameter is more preferably 0.02 to 3 μm, and even more preferably 0.05 to 1 μm, from the viewpoints that finer and finer voids are expressed, light weight is excellent, and fiber properties are homogenized. . 0.05-1 μm is particularly preferable.

  Further, the ratio (R / r) between the average maximum dispersed diameter (r) and the diameter of the fiber single yarn cross section (R; in other words, the single fiber diameter) is such that more voids are formed or the fiber properties are excellent. In the above, R / r is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more.

As described above, the hollow blend fiber of the present invention needs to have a void in at least a part of the blend interface between component A and component B (see FIG. 2). Having the voids makes the hollow blend fiber of the present invention extremely excellent in lightness and is preferable, and can also have excellent light shielding properties derived from light diffusibility as described above. Further, since the voids are fine, it is difficult to become a defect in the fiber structure and the fiber strength is excellent. The porosity indicates the ratio of the voids in the fiber for (Va) from the viewpoint of the hollow blend fibers of the present invention is excellent in more lightweight, it is preferred that Va is 15% or more, 25% or more It is more preferable that In addition, having a void in at least a part of the blend interface between component A and component B is a platinum-palladium vapor deposition (deposition) with an acceleration voltage of 10 kV using a scanning electron microscope ESEM-2700 manufactured by Nikon Corporation. (Membrane pressure: 25 to 50 angstroms) After the treatment, it was confirmed at an arbitrary magnification of 200 to 100,000 magnifications. The sample was prepared by cooling the fiber and blade used as a sample in liquid nitrogen, cutting the fiber cross section perpendicular to the fiber axis direction in liquid nitrogen to be an observation surface after cooling for 15 minutes, or Or it can confirm by observing the sample which carried out the embedding | embedding and performed the end surface of the fiber cross section perpendicular | vertical to a fiber-axis direction with an ultramicrotome.

As method for expressing a void of the hollow blend fibers of the present invention, for example, stress may be a method capable of expressing applying to voids and stretching To illustrate, the undrawn yarn obtained by winding at spinning at high magnification In addition to the method of drawing, the method of drawing continuously at a high magnification without winding up the undrawn yarn at the time of spinning, the method of taking up at a high speed in spinning, or by heating the obtained yarn or irradiating with specific light And a method of shrinking component B in the hollow blend fiber, and any method can be employed, but the process was simple and the formation of voids was easy to control. A method of stretching an undrawn yarn at a high magnification or a method of continuously drawing at a high magnification without winding up the undrawn yarn at the time of spinning is preferred.

The hollow blend fiber of the present invention needs to have a hollow portion communicating in the fiber axial direction (see FIG. 2). When the hollow blend fiber of the present invention does not have the hollow part, it has lightness depending on the gap as described above, but its weight reduction is naturally limited, and various physical properties such as lightness or strength intended by the present invention are achieved. It is not preferable for the fiber to bear. However, since the hollow blended fiber of the present invention is further provided with the light weight of the hollow portion by having the hollow portion, the hollow blend fiber can have a very favorable characteristic that the light weight is remarkably improved. The hollow ratio indicating the amount of the hollow section for (Vb), in that the hollow blend fibers of the present invention is more excellent in light weight, Vb is that preferably 10% or more, 20% or more More preferably, it is still more preferably 30% or more. The number of the hollow portion in a cross section perpendicular to the fiber axis direction of the single fiber is one or two or more of may have a plurality, hollow portion is hardly collapsed, also improve the aforementioned light-diffusing The number of hollow portions is preferably 2 or more, more preferably 4 to 2000, still more preferably 6 to 500, and more preferably 10 to 100 in that it can be caulked. It is particularly preferable that the number is individual.

As the shape of the hollow portion, round, polygonal type, multi other wafer type etc. are suitably employed depending on the purpose, or the central hollow portion and the fiber portion toward the monofilament from monofilament outer peripheral portion Alternately, the layers may be formed concentrically or eccentrically. Further, the hollow blend fiber of the present invention may have the same or different shape of the plurality of hollow portions in the cross section of the single fiber, or the shape of the hollow portion is single fiber if the present invention is a multifilament. They may be the same or different. Furthermore, since the size of the hollow portion is preferably smaller as compared with the single yarn diameter of the fiber, it is preferably 3/4 or less of the single fiber diameter in the cross section perpendicular to the fiber axis direction of the single fiber. It is more preferable that it is 1 or less, and it is more preferable that it is 1/3 or less. Here, the single fiber diameter means a fiber diameter passing through the apparent center of the cross section if the fiber has a round cross section, and if it has a cross sectional shape other than the round shape, the single fiber has the shortest diameter. This is regarded as the single fiber diameter. Alternatively, the maximum diameter of the hollow portion is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 1 μm or less. Here, the maximum diameter of the hollow part means a hollow part diameter passing through the apparent center of the hollow part if the hollow part has a round cross section, and hollow if the hollow part has a cross-sectional shape other than the round shape. The size of the longest diameter of the part is regarded as the maximum diameter of the hollow part.

As a method for forming the hollow portion, for example, or to obtain a hollow fiber in the form of a spinning discharge port to discharge shape as to be able to form a hollow, such as a circle with a slit, an aqueous solution or hot water or organic, A blend composition comprising component A and component B that form the hollow blend fiber of the present invention using a component that can be eluted using a reagent such as a solvent (hereinafter sometimes referred to as "eluting component") as a core component or an island component. Is obtained by obtaining a core-sheath composite fiber or sea-island composite fiber and then eluting the elution component, which is a core component or island component, to obtain hollow fibers, and further, component A and component B And a method of preparing a three-component blend composition by blending the elution component with a blend composition comprising: and performing melt spinning to obtain a hollow fiber by eluting the elution component. That although, in terms of capable of maintaining without form of a hollow part is collapsed in order processing of the fibers, a method of obtaining a hollow fiber eluting the elution component forming the core component or the island component.

As a means of producing hollow blend fibers of the present invention, illustrating a more specific preferred methods are described below.

The hollow blend fiber of the present invention is an aqueous solution because it has the advantages that the process is very simple, excellent in productivity, and the cross-sectional shape of the fiber can be freely controlled in a variety of fiber production methods. A core-sheath composite type in which a component that can be eluted using a reagent such as water, hot water, or an organic solvent is a core component, and a blend composition composed of component A and component B forming the hollow blend fiber of the present invention is a sheath component Alternatively, it is preferably a sea-island composite-type melt spinning using the aforementioned eluting component as an island component and the blend composition as a sea component. Here, in the core-sheath composite, the ratio of the core to the sheath that determines the size of the hollow portion is preferably core: sheath = 10: 90 to 80:20, and more preferably 20:80 to 70:30. In the sea-island composite, the number of islands that form a hollow portion after being eluted in the subsequent step is preferably 2 or more, preferably 4 to 2000, more preferably 6 to 500. Even more preferably, it is ˜100. The size of the island may be appropriately determined depending on the number of islands, but is preferably 3/4 or less of the single fiber diameter, more preferably 1/2 or less. It is more preferable that it is 1 or less. In addition, examples of the shape of the island (or core) include a round shape, a polygonal shape, and a multi-leaf shape. In particular, the structure that forms the island has a specific structure from the outer periphery of the single fiber to the center of the single fiber. Alternatively, the islands and the sea may alternately form layers concentrically toward the surface. In addition, when having a plurality of the islands in the fiber cross section perpendicular to the fiber axis direction of one core-sheath composite spun yarn or sea-island composite spun yarn, the shape of the islands may be the same or different, Alternatively, if the core-sheath composite spun yarn or the sea-island composite spun yarn is a multifilament, the shape of the island may be the same or different between the single fibers. Alternatively, the maximum diameter of the island is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 1 μm or less. Here, the maximum diameter of the island means an island diameter passing through the apparent center of the island if the island has a round cross section, and the maximum diameter of the island if the island has a cross-sectional shape other than the round shape. Consider size as the maximum diameter of the island.

  In melt spinning, the core-sheath composite spun yarn or sea-island composite spun yarn discharged from the die hole is cooled below the glass transition temperature of the polyester of the present invention, and at a take-up speed of 100 to 10,000 m / min, preferably 4000 m / min. It is taken up at a take-up speed of not more than minutes, more preferably not more than 3000 m / min, even more preferably not more than 2500 m / min, particularly preferably not more than 2000 m / min.

  After taking up, after winding up, or after winding up, without heating or heating, preferably heated to a temperature below the glass transition temperature (Tgb) of component B, more preferably of component A Glass transition temperature (Tga) −20 ° C. to Tgb is heated to a temperature range of natural drawing ratio or higher, preferably 1.5 times or higher, more preferably natural drawing ratio or higher. It is stretching at a magnification at which the elongation becomes 3 to 50%, and even more preferably at a magnification at which the residual elongation of the drawn yarn is 10 to 40% or more than the natural stretching magnification. Here, after stretching once (that is, after finishing the first-stage stretching), the second-stage stretching may be performed at a magnification of 2 times or less.

  A method of heat treatment at a temperature of Tga + 10 ° C. or higher after stretching is preferred. This is because the voids become larger by stretching at a high magnification, and the composite fiber obtained by the present invention is extremely excellent in lightness, but the area around the voids that is developed by heat treatment after stretching is heated. It is fixed and can impart light weight with excellent heat resistance. Here, the heat treatment performed after stretching is preferably performed at a temperature lower than the melting point of Component B so that the developed voids are not crushed.

Above for stretching method or a heat treatment method after stretching, because of high heating efficiency, the heated pin-like material, when using a contact type bath using a contact type heater or heated liquid such as Plate-like material In addition, it is preferable that the undrawn yarn is easily deformed at the same time that the undrawn yarn reaches a deformable temperature.

Core-sheath composite spinning yarn or island composite spinning yarn described above, it pulled up by the melt spinning, after winding without or once the wound may be false twisting to then subjected to extension Shin. In the false twisting process, the composite fiber is heated by a contact-type or non-contact-type method and drawn by a disk-like object, a belt-like object, or a pin-like object when using drawn yarn. When undrawn yarn is used, it is similarly twisted with a disk-like material, a pin-like material, or a belt-like material while being drawn with or without being heated by a contact-type or non-contact-type heater. Processed. Although the false twisted composite fiber can be wound as it is, it is preferably wound after being heat set.

  After undergoing the above-described drawing or false twisting process, the core-sheath composite spun yarn or sea-island composite spun yarn obtains the hollow blend fiber of the present invention in which a hollow portion is formed by removing the elution component which is the core component or the island component. . As described above, the elution component is eluted using a reagent such as water, hot water, an aqueous solution in which other organic and / or inorganic compounds are dissolved, an organic solvent, or a mixed liquid selected from these. It is preferable that it can be removed, and it is more preferable to elute with an aqueous solution in which water, hot water, and other organic and / or inorganic compounds are dissolved.

Preferred examples of the elution component include readily alkali-soluble polyester, hot water-soluble polyester, polyethylene glycol, polyethylene oxide, water-soluble thermoplastic polyvinyl alcohol or ethylene-vinyl alcohol copolymer, and polysaccharide compounds. Depending on the type of polymer forming the hollow blend fiber of the present invention, it can be employed as appropriate. And since the handling in melt spinning is easy, the hot water soluble polyester which melt | dissolves in an easily alkali-soluble polyester and hot water is more preferable.

  In the present invention, since component A and component B are a combination of incompatible polymers, the compatibility may be poor. Therefore, the hollow blend fiber composed of component A and component B preferably contains a compatibilizer for component A and component B. The compatibilizing agent in the present invention is an additive that reduces the size of the domain of component B by changing the interaction at the blending interface when blending component A and component B to increase the compatibility of both. It is. As the compatibilizing agent, a wide variety of compounds such as a low molecular compound or a high molecular compound can be adopted. For example, as the low molecular compound, sodium dodecylbenzenesulfonate, sodium alkylsulfonate, glycerin monostearate, Anionic or cationic surfactants such as tetrabutylphosphonium paraaminobenzenesulfonate and amphoteric surfactants, poly (alkylene oxide) glycols such as polyethylene glycol, methoxypolyethylene glycol, polytetramethylene glycol, and polypropylene glycol, and ethylene oxide / propylene Nonionic surfactants, such as an oxide copolymer, are mentioned.

  Moreover, as a high molecular compound mentioned as a compatibilizing agent, what is necessary is just to use a high molecular compound with high compatibility or affinity with respect to each of component A and component B, for example, a polystyrene polymer, a polyacrylate polymer, Polymethacrylate polymers, poly (vinyl alcohol-ethylene) copolymers, poly (vinyl alcohol-propylene) copolymers, poly (vinyl alcohol-styrene) copolymers, poly (vinyl acetate-ethylene) copolymers, poly (vinyl acetate-propylene) copolymers, Vinyl polymers or copolymers such as poly (vinyl acetate-styrene) copolymers, ionomers, polysaccharides, polyalkylene oxides or poly (alkylene oxides) that have improved heat resistance and melt plasticity by chemically modifying the side chain moiety. Copolymers of alkylene oxides and vinyl derivatives, such as poly (alkylene oxide-propylene) copolymers, polyalkylene oxide derivatives, copolymers of alkylene terephthalate and alkylene glycol, copolymers of alkylene terephthalate and poly (alkylene oxide) glycol And polymers such as copolymers, copolymers of alkylene terephthalate and polyalkylene diols, and the like. Among them, considering that the effect as a compatibilizing agent is great and the yarn physical properties are good when the hollow blend fiber obtained in the present invention is formed, polystyrene polymer, polyacrylate polymer, polymethacrylate polymer are considered. , Copolymers of styrene and methyl methacrylate, copolymers of alkylene terephthalate and alkylene glycol, copolymers of alkylene terephthalate and poly (alkylene oxide) glycol, poly (alkylene oxide) glycol, copolymers of alkylene terephthalate and polyalkylene diol, or derivatives of these polymers Is preferred.

Below, the preferred alkylene terephthalate seems a polyalkylene diol, copolymers of alkylene terephthalate and alkylene glycol, we describe a specific example of alkylene terephthalate and poly copolymers of (alkylene oxide) glycol or a poly (alkylene oxide) glycol or a derivative thereof .

As a copolymer of alkylene terephthalate and polyalkylene diol, an alkylene terephthalate selected from ethylene terephthalate, propylene terephthalate, butylene terephthalate, pentamethylene terephthalate, hexamethylene terephthalate, etc., and polyalkylene diol selected from polyethylene diol, polybutylene diol, etc. One type of each of alkylene terephthalate and alkylene glycol may be used, or a plurality of types may be used. In concrete terms, poly (ethylene terephthalate - polyethylene diol) copolymers, poly (propylene terephthalate - polyethylene diol) copolymers, poly (butylene terephthalate - polybutylene diol) copolymers, and the like.

As the copolymer of alkylene terephthalate and alkylene glycol, alkylene terephthalate selected from ethylene terephthalate, propylene terephthalate, butylene terephthalate, pentamethylene terephthalate, hexamethylene terephthalate, ethylene glycol, propylene glycol, butylene glycol (or tetramethylene glycol), penta It is a copolymer comprising an alkylene glycol selected from methylene glycol and hexamethylene glycol, and one or more of each of alkylene terephthalate and alkylene glycol may be used. In concrete terms, polyethylene terephthalate - can be exemplified tetramethylene glycol copolymer, etc. - butyl les glycol copolymer, polypropylene terephthalate - ethylene glycol copolymer, polybutylene terephthalate.

As the copolymer of alkylene terephthalate and poly (alkylene oxide) glycol, alkylene terephthalate selected from ethylene terephthalate, propylene terephthalate, butylene terephthalate, pentamethylene terephthalate, hexamethylene terephthalate, and the like, diethylene glycol, triethylene glycol, poly (ethylene oxide) glycol, A copolymer comprising poly (alkylene oxide) glycol selected from dipropylene glycol, poly (propylene oxide) glycol, poly (ethylene oxide-propylene oxide) glycol composed of a copolymer of ethylene oxide and propylene oxide, and alkylene terephthalate And 1 each of poly (alkylene oxide) glycol It may be used by classes, or may be used in combination. In concrete terms, polyethylene terephthalate - can be exemplified poly (ethylene oxide) glycol copolymers and the like - diethylene glycol copolymers, polyethylene terephthalate - poly (ethylene oxide) glycol copolymer, polybutylene glycol - poly (ethylene oxide) glycol copolymers, polypropylene terephthalate.

The main chemical structure of poly (alkylene oxide) glycol or its derivative is a group (or group) of aliphatic, aromatic, alicyclic, etc. carbon having a main chain and oxygen atoms bonded alternately. Any poly (alkylene oxide) glycol having a single alkylene oxide represented by the following general formula (X) as a repeating unit may be used.
− [(CH ₂ ) _a —O] _m − (X)
Examples of satisfying the formula (X) include poly (ethylene oxide) glycol (a = 2), poly (propylene oxide) glycol (a = 3), poly (tetramethylene oxide) glycol (a = 4), and the like. Of poly (alkylene oxide) glycols.

The poly (alkylene oxide) glycol may be an alternating, random or block copolymer of different alkylene oxides as represented by the following general formula (Y).
_{- {[(CH 2) a} -O] m - [(CH 2) b -O] n} x - ··· (Y)
As satisfying the formula (Y), for example, a poly (oxyethylene-oxypropylene) copolymer (a = 2 or 3, b = 2 or 3, and a and b may be the same or different. ), Poly (oxytetramethylene-oxyethylene-oxypropylene) copolymer (a = 1 or 2 or 3, b = 1 or 2 or 3, and a and b may be the same or different.) For example, copolymers of different alkylene oxides.

  Furthermore, as the poly (alkylene oxide) glycol, the polyalkylene oxide represented by the general formula (X) or (Y) may be one kind alone, or in a range not impairing the gist of the invention. You may use what combined 2 or more types in the range which does not impair the main point of invention.

  As the compatibilizing agent content in the hollow blend fiber of the present invention, the blend of component A and component B is more effectively refined, and the voids of the resulting hollow blend fiber are refined, resulting in excellent fiber properties. In this respect, the content of the compatibilizing agent is preferably 2 to 500% by weight, more preferably 5 to 400% by weight, based on the content of Component B.

As the method of adding the compatibilizer in the hollow blend fibers of the present invention, any one of the known methods is added to the blend composition of the components A and B in any previous stage of melt spinning is completed, for example, (a) In a usual polymerization reaction of component A, a method of adding and melting and kneading at an arbitrary stage before the polymerization reaction stops, (b) a compatibilizer in a composition obtained by blending component A and component B prepared in advance. Add and add a specified amount of compatibilizer, component A and component B simultaneously to a kneader such as an extruder or static mixer during melt spinning, using a kneader such as an extruder or static mixer. and a method of melt-kneading at atmospheric pressure or under reduced pressure, and the like, a method of the aforementioned in terms of operability (b) or (c) are preferably employed

For the fiber diameter of the hollow blend fibers of the present invention is excellent in fiber properties, or in that processability is improved in forming a fabric, it is preferable that the fiber diameter is 0.01～5000Myuemu, more preferably Is 1000 μm or less, and more preferably 200 μm or less. In addition, as for the outer diameter cross-sectional shape of the fiber , for example, a round shape, a polygonal shape, a multi-leaf shape, and the like can be cited as long as the material has the above-described hollow portion. Or, in terms of further improving the lightness, a polygonal shape or a multileaf shape is preferable. The number of single fibers in a single yarn also may be appropriately set according to the intended use, such as apparel applications or industrial materials, for example, one monofilament may be, or two or more of the plurality of yarns A multifilament made of may be used. In particular, in the case of multifilaments, it is preferably 2 to 2000, and more preferably 4 to 500, taking into consideration the spinning performance in the spinning or drawing process and the process passability in higher processing. Preferably, it is more preferably 4 to 250.

Hollow blend fibers of the present invention, the form stability and weather resistance is excellent, or in that it employs the shrinkage characteristics in various use environments in various materials for clothing or industrial hot water or boiling water (about 70 100%), the shrinkage rate when held for 15 minutes is preferably 50% or less, more preferably 30% or less, and even more preferably 25% or less.

The hollow blend fibers of the present invention, in addition to the shape stability is excellent, in view of the allowable deformation of the various materials for clothing or industrial, that elongation of the fibers at 20 ° C. is not more than 100% Is preferably 60% or less, more preferably 45% or less.

  The hollow blended fiber of the present invention preferably has an apparent specific gravity of 1.2 or less from the viewpoint that it is more lightweight. When the apparent specific gravity is 1.2 or less, not only when it is used as clothing for infants or elderly people, but also when used as sports uniform or outdoor clothing, it has excellent bulkiness and light weight. Is preferable. Further, when used as an industrial material, for example, assuming that the composite fiber of the present invention is compared with a synthetic fiber obtained by ordinary melt spinning and stretching, it is assumed that the same strength is assumed. Since the total weight of the composite fiber is small, it is very preferable for transportation, for example. On the contrary, when the above two types of fibers have the same weight and the strength that can be carried is compared, the composite fiber of the present invention It is a very good material that can carry greater strength. The apparent specific gravity of the composite fiber is more preferably 1.0 or less, and even more preferably 0.95 or less.

The fiber blend strength is preferably 3.5 cN / dtex or more in that the hollow blend fiber of the present invention can be widely used for clothing or industrial materials. Of course, when used as clothing for infants or the elderly, as well as when used as sports uniforms or outdoor clothing, and when used as industrial material, it should be strong in terms of fiber strength. Is preferable from the viewpoint of application development. Also, when considering the workability of the fiber or fabric, the yarn physical properties are required to have high strength in that the variation of processing is widened. The strength of the composite fiber is 4 . It is favorable preferable to further is 0cN / dtex or more.

The hollow blend fiber of the present invention has both a fine void and a hollow portion, so it is very excellent in light weight , and the total porosity indicating the degree of total void in the hollow blend fiber formed from the void and the hollow portion. (V) is preferably 25% or more, more preferably 30% or more, even more preferably 40% or more, and particularly preferably 50% or more. Here, the total porosity (V;%) indicates the apparent specific gravity of the present invention according to Example E.E. The void ratio (Vb;%) indicating the amount of the hollow portion and the void ratio (Va;%) indicating the amount of voids described above can also be calculated by measuring by the above method. It can be calculated from the method shown in

  The hollow blended fiber of the present invention has a matting agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, an infrared ray in the component A part, the component B part, the void part or the hollow part as long as the gist of the invention is not impaired. A small amount of additives such as an absorbent, a crystal nucleating agent, a fluorescent brightening agent, and a terminal group blocking agent may be retained.

  The hollow blend fiber of the present invention is very useful as a fiber itself because it is excellent in light weight, and the fiber can be used as it is. However, since it is excellent in light weight, the hollow blend fiber of the present invention is used as a fiber product. You may use for a part or all. Textile products in which the hollow blended fiber of the present invention is used in part or in whole include fabrics such as taffeta, twill, satin, desine, palace, and georgette, flat knitting, rubber knitting, double knitting, single tricot knitting, Shows knitted fabrics such as half tricot, chemical bond method, thermal bond method, needle punch method, water jet punch (spun lace) method, stitch bond method, felt method, etc. There are no particular restrictions on the form of fibers such as processed yarn. Of course, if it is a woven or knitted fabric, it may be processed by conventional scouring, dyeing, heat setting, etc., or if it is a non-woven fabric, it may be a glazing press, embossing press, compact processing, flexible processing, heat setting, etc. Chemical processing such as physical processing, bonding processing, laminating processing, coating processing, antifouling processing, water repellent processing, antistatic processing, flameproofing processing, insectproof processing, sanitary processing, foam resin processing, etc. In addition, application processing such as microwave application, ultrasonic application, far-infrared application, ultraviolet application, and low-temperature plasma application may be performed, and the final form may be sewn as clothing.

The fiber product in which the hollow blend fiber of the present invention is used in part is a synthetic fiber, semi-synthetic fiber, natural fiber, etc. different from the hollow blend fiber of the present invention, such as cellulose fiber, wool, silk, etc. A mixed fiber product (hereinafter sometimes referred to as a mixed product) characterized by using at least one type of fiber selected from stretch fiber and acetate fiber. A specific example, as the cellulose fibers, cotton, natural fibers hemp, steel ammonia rayon, rayon, polynosic, and the like, for the content of the hollow blend fibers mix with these cellulose fibers, cellulose fibers In order to make use of the texture, moisture absorption, water absorption and antistatic properties of the present invention and to make use of the light weight of the hollow blend fiber of the present invention, 25 to 75% is preferable. In addition, the existing wool and silk used in mixed products can be used as they are. The content of these wool or hollow blended fibers mixed with silk is the texture, warmth, bulkiness of the wool, In order to make use of the texture and squeak noise and to make use of the light weight of the hollow blend fiber of the present invention, 25 to 75% is preferable. The stretch fiber used in the mixed fabric is dry spun or melt spun polyurethane fibers, polyester-based elastic yarn comprising such as polybutylene terephthalate fibers and polytetramethylene glycol copolymerized polybutylene terephthalate fibers and the like, stretch In a mixed article using fibers, the content of hollow blend fibers is preferably about 60 to 98%. When the content of the hollow blend fiber exceeds 85%, the stretchability can be suppressed, so that it can be used for outer and casual wear applications. If it is less than 70%, it can be used for innerwear, foundation, swimwear, etc. due to its stretchability. Further, acetate fiber used in the mixed fabric may be a triacetate fibers at diacetate fibers. The content of the hollow blend fiber mixed with these acetate fibers is preferably 25 to 75% in order to make use of the texture, sharpness and gloss of the acetate fiber and to take advantage of the light weight of the hollow blend fiber of the present invention.

In these various mixed fabric, the form of a hollow blend fibers of the present invention, the mix method may be any known method. For example, mixed methods include woven fabrics such as union woven fabrics and reversible fabrics used for warp or weft yarns, knitted fabrics such as tricot and russell, and other knitting, doubling, and entanglement may be performed.

  The textile product of the present invention may be dyed including mixed goods. For example, after knitting and weaving, it is preferable to carry out processes of scouring, pre-setting, dyeing and final setting by a conventional method. Further, if necessary, it is also preferable to carry out an alkali reduction treatment by a conventional method after scouring and before dyeing. The scouring is preferably performed in a temperature range of 40 to 98 ° C. In particular, in the case of blending with stretch fibers, it is more preferable to refine the blended articles while relaxing the blended articles because the elasticity is improved. One or both of the heat sets before and after dyeing can be omitted, but it is preferable to perform both in order to improve the form stability and dyeability of the mixed product. The heat setting temperature is 120 to 190 ° C., preferably 140 to 180 ° C., and the heat setting time is 10 seconds to 5 minutes, preferably 20 seconds to 3 minutes.

Hereinafter, the present invention will be described specifically and in detail by way of examples. The present invention, as illustrated in the component A, (sometimes hereinafter abbreviated as PET) polyethylene terephthalate as a polyester-based polymer, and also that describes an embodiment taken nylon 6 as the polyamide-based polymer. In addition, the physical-property value in an Example was measured with the following method.

A. Measurement of Melt Viscosity Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., under a nitrogen atmosphere, the barrel diameter was 9.55 mm, the nozzle length was 10 mm, the nozzle inner diameter was 1 mm, and the shear rate was 10 sec ⁻¹ . And the average value of the value measured 5 times was made into the measured value of melt viscosity. Regarding measurement time, 5 measurements were completed within 30 minutes in order to prevent deterioration of the sample.

B. Measurement of glass transition temperature (Tg) and melting point (Tm) Using a differential scanning calorimeter (DSC-2) manufactured by PerkinElmer, the glass transition temperature (Tg) was measured at a heating rate of 16 ° C./min. The definitions of Tm and Tg are as follows. After observing the endothermic peak temperature (Tm ₁ ) observed once measured at a heating rate of 16 ° C./min, the temperature is kept at a temperature of about (Tm ₁ +20) ° C. for 5 minutes. Rapidly cool to room temperature (hold for 5 minutes by combining the quenching time and room temperature holding time) and measure the endothermic peak temperature as Tg as a stepwise baseline deviation when measured again at 16 ° C / min. The endothermic peak temperature observed as the melting temperature of the crystal was defined as Tm.

C. In a film comprising component A or component B for measuring the critical surface tension γ _c , pure water 72.8 dyne / cm, ethyl alcohol (special grade or higher) 22.3 dyne / cm, dioxane 33.6 dyne / cm, hexane 18.4 dyne / cm , 20% ammonia water 59.3 dyne / cm, one droplet on a sample having a flat surface to be measured under the conditions of 20 ° C., humidity 40-80%, and standing When the droplet is stationary, the angle formed by the solid plane in contact with the droplet and the surface of the droplet in contact with the air layer is measured as the contact angle θ, and the surface tension of the liquid used is measured. plotting the against cos [theta] (Zisman plot), fully wetted, i.e., the critical surface tension gamma _c by extrapolating the points obtained by plotting the surface tension when the cos [theta] = 1 Meta.

D. Fiber strength, measurement of residual elongation, setting of natural draw ratio Using an Tentecron tensile tester (TENSIRON UCT-100) manufactured by Orientec, if it is an undrawn yarn, it is drawn at an initial sample length of 50 mm and a pulling speed of 400 mm / min. In the case of a yarn, the strength and the residual elongation were measured at an initial sample length of 200 mm and a tensile speed of 200 mm / min, and the average value measured five times was used as each measured value. The natural draw ratio is obtained by dividing the elongation (%) at which the constant stress elongation region is completed by 100 in the stress-strain curve (SS) obtained when measuring the strength and elongation of the undrawn yarn. The value obtained by adding 1 was taken as the natural stretch ratio.

E. Measurement of Apparent Specific Gravity and Calculation of Total Porosity, Porosity, and Hollow Ratio The apparent specific gravity of the fiber was measured and calculated by the following method.
(A) When the apparent specific gravity of the fiber is 0.659 or more, 20 ° C. based on the float / sink method defined in JIS-L-1013: 1999 8.17.1 (published by the Japanese Standards Association, chemical fiber filament yarn test method) Under a temperature of ± 5 ° C., a NaBr aqueous solution is used as the solvent if the specific gravity is 1 or more, and an ethyl alcohol aqueous solution is used if the specific gravity is between 1 and 0.789, and the specific gravity is 0.789 to 0.00. If it is between 659, using an ethyl alcohol-hexane solution, a liquid having a specific gravity in which the yarn does not float or sink for 24 hours is prepared and measured, and an average value of five specific gravity values is measured as a specific gravity value ( Q).
(B) When the apparent specific gravity of the fiber is less than 0.659: 100 g ± 10 g of the following K.I. Weighed in advance using the tubular knitted fabric prepared by the method described in 1. In addition, we fixed the weight of which weight and volume were known in advance to the tubular knitted fabric, and added it to ion-exchanged water prepared at 4 ° C ± 1 ° C. After submerging and defoaming with ultrasonic waves for 5 minutes, the volume of the tubular knitting was measured, and the average value of the specific gravity values of 10 fabrics was defined as the measured specific gravity value (Q).
Further, the total porosity (V;%) representing the total amount of voids and hollow portions in the fiber is measured according to the following formula, and the apparent specific gravity (R: calculated from the following formula) and measurement of the blend fiber when there are no voids and hollow portions. The specific gravity value Q was used for calculation.
Total porosity (V;%) = 100 (1-Q / R),
Apparent specific gravity R of the composite fiber without voids and hollows;
R = 100 / ((100-S1-S2) / V + S1 / V1 + S2 / V2),
[V: density of component A (g / cm ³ ), S1: weight% of component B in fiber]
V1: density of component B (g / cm ³ ), S2: weight% of compatibilizer in fiber (S2 = S1 × [wt% relative to S1] / 100), V2: density of compatibilizer (g / cm ³ )
In addition, about each density of a component A, a component B, and a compatibilizing agent, the nominal value of a manufacturer is used as it is, or the density gradient tube of JIS-L-1013 using the undrawn yarn or drawn yarn which consists of each component independently. The value measured by the method was used. For example, when component A is PET, 1.34 is used for undrawn yarn, and 1.38 is used for drawn yarn.

Furthermore, the void ratio (Va;%) or the hollow ratio (Vb;%) of each obtained fiber was calculated according to the following methods E-1 and E- 2.

<E-1: Calculation method of porosity (Va;%)>
In the following examples, the fiber specific gravity before and after stretching that causes voids was measured by the float / sink method of JIS-L-1013, Va (%) = [fiber specific gravity after stretching] / [specific gravity of fiber before stretching] × 100.

<E-2; Calculation method of hollow ratio (Vb;%)>
In the following examples, when performing melt spinning using a modified cross-section die, the cross-sectional photograph of the obtained drawn yarn is digitally photographed, and the area ratio occupied by the hollow portion in the single-fiber apparent fiber cross-sectional area for 100 yarns, In the computer software WinROOF (version 2.3) manufactured by Mitani Shoji Co., Ltd., calculated from the fiber outer diameter and the fiber hollow inner diameter, the area ratio (average value) is multiplied by 100 and the hollow ratio (average hollow ratio) Vb did. When a core or island is leached from a core-sheath fiber or sea-island fiber to obtain a hollow fiber, the fiber specific gravity before and after leaching is measured by the float / sink method of JIS-L-1013, and Vb (%) = ([Leaching The specific gravity after fiber] / [specific gravity of fiber before leaching]) × 100.

F. Measurement of fiber diameter (R), component B incompatibility, average dispersion diameter, average maximum dispersion diameter (r) Nikon Corporation, using scanning electron microscope ESEM-2700, acceleration voltage 10 kV, The sample was subjected to platinum-palladium vapor deposition (deposition film pressure: 25 to 50 angstrom), and then confirmed at an arbitrary magnification of 200 to 100,000 times. The sample was prepared by cooling the fiber and blade used as a sample in liquid nitrogen, cutting the fiber cross section perpendicular to the fiber axis direction in liquid nitrogen to be an observation surface after cooling for 15 minutes, or Or the sample which carried out the embedding | embedding and performed the end surface of the fiber cross section perpendicular | vertical to a fiber axis direction with the ultramicrotome was used for observation. For the average domain size of component B, see E. The cross-sectional photograph was digitally taken in the same manner as in the above section, and the average area value of all the components B existing on the cross section of the fiber was calculated in the computer software WinROOF (version 2.3) manufactured by Mitani Corporation. From this, the average diameter of the domain (domain size) was calculated.

G. Confirmation of discontinuity of component B (dispersion length of component B in the direction of fiber axis) 0.1 g of composite fiber obtained was impregnated in 200 ml of 0.1N aqueous sodium hydroxide solution and stirred at 50 ° C. for 24 hours. Then, the component A PET was hydrolyzed. The suspended matter floating on the surface of the aqueous solution was collected with a dropper, dropped onto a glass slide washed with ethanol, sandwiched between cover glasses, and observed with an optical microscope at about 100 to 600 times. For those that cannot be observed with an optical microscope, remove the suspended matter in front of F.C. The specimen was observed under a water vapor atmosphere of 600 Pa using the item ESEM-2700. Then, as an evaluation of blendability, the ratio β / α of the diameter (α) and the length (β) of the component B is obtained, and the maximum observable ratio is used as an index of the dispersion length of the component B. ◯ when it is, and X when it is larger than 1,000.

H. Evaluation of stretchability About stretchability, 10kg drawn yarn is prepared and evaluated by the average number of single yarn breaks per kg, and when single yarn winding occurs frequently and cannot be drawn or the number of times the single yarn is wound is More than 10 times were evaluated as △ (inferior), the number of times that the single yarn was wound was 3 or more and less than 10 times, ○ (good), and the number of times that the single yarn was wound was evaluated as double circle (excellent).

I. Measurement of weight average molecular weight High performance liquid chromatograph LC-6A manufactured by Shimadzu Corporation (differential refractometer RID-6A, pump LC-9A, column oven CTO-6A, columns Shim-pack GPC-801C, -804C, -806C , -8025C), and obtained by measuring at a column temperature of 40 ° C. using chloroform (flow rate: 1 mL / min, sample amount: 200 μL (however, 0.5 w / w% sample dissolved in chloroform)) as a solvent. .

J. et al. The intrinsic viscosity (IV) measurement sample was dissolved in an orthochlorophenol solution and measured at 25 ° C. using an Ostwald viscometer.

K. A cylindrical knitted fabric having a gauge width of 20 / 2.54 cm and a pitch length of 1 mm was prepared as a light-shielding evaluation sample. Eight pieces of this fabric were overlaid on a 5 × 5 cm sample plate. A sample was confirmed by visual observation that the color did not show through. And the spectral transmittance characteristic about the wavelength range of 0.36-0.74 micrometer with respect to the standard white board of this sample was measured in the transmittance | permeability measurement mode of the spectrocolorimeter (Minolta Co., Ltd. CM-3700d), and each sample The maximum spectral transmittance in the wavelength range is obtained from the spectral transmittance characteristics obtained by averaging the measurement results obtained three times for each measurement location and three times at different measurement locations, and the maximum transmittance in the wavelength range is determined. Those having a value of 10% or more were evaluated as Δ (inferior), those having a value of 5% or more but less than 10% as ○ (good), and those having a value of less than 5% as ◎ (excellent).

Reference Example 0.03 parts by weight of 85% aqueous solution of phosphoric acid as a coloring inhibitor and 0.03 part by weight of a polycondensation catalyst were added to a low polymer obtained by ordinary esterification reaction from 166 parts by weight of terephthalic acid and 75 parts by weight of ethylene glycol. A polycondensation reaction was carried out by adding 0.06 parts by weight of antimony and 0.06 parts by weight of cobalt acetate tetrahydrate as a toning agent, and the commonly used IV 0.70, melt viscosity 2050 poise (290 ° C., shear rate 10 sec) ^-1 ) polyethylene terephthalate (hereinafter referred to as PET).

  Using this PET, melt spinning is performed using a biaxial extruder type melt spinning machine using a round hole-shaped die having a spinning diameter of 290 ° C., a hole diameter of 0.3 mm, and 24 holes. 1200 m A polyester multifilament fiber having a round shape of 292 dtex-24 filaments was obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  When the obtained polyester fiber is stretched, the yarn feeding speed of the yarn feeding roller is 100 m / min, the first roller is not heated (room temperature), the yarn feeding speed is 100 m / min, and the yarn feeding speed of the second roller is 350 m / min. In order to perform stretching between the first roller and the second roller, a 100 ° C hot plate was used as a heat source, the stretching ratio was 3.5, and the second roller was 150 ° C to heat-treat the fibers. Thereafter, the yarn was cooled with a cold roller to Tg or less of the polyester and wound up. No thread breakage occurred during drawing, and the drawability was excellent. The spinning conditions of the reference examples are shown in Table 1, and the yarn properties are shown in Table 2.

Reference example 1
When performing melt spinning using a biaxial extruder type melt spinning machine using the polyester obtained in the reference example, as a component B, polymethylpentene (TPX, type RT18, manufactured by Mitsui Chemicals, Inc.) A blend polymer prepared by adding 8% by weight of PMP) is used as a sea component in composite spinning, and 20 mol% of isophthalic acid and 15 mol% of a sodium sulfonate derivative of isophthalic acid are used together. Polymerized IV0.51 hot water-soluble copolymerized polyethylene terephthalate (hereinafter abbreviated as hot water-soluble PET) is used as an island component in composite spinning, so that sea: island = 65: 35 and the number of islands is four. The sea-island composite spinning was performed on the other, and the other 305 dtex-24 filaments had a round cross-sectional shape under the same spinning conditions as in the reference example. To give the ester composite multi-filament fibers. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 3.3 times in the same manner as in the reference example. Although the single yarn breakage occurred 4.5 times during drawing, the drawability was good.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. A void was observed at the interface between component A (polyester) and component B (PMP). The results of Reference Example 1 are shown in Table 2.

Reference example 2
When the polyester obtained in the Reference Example was melt-spun using a twin-screw extruder type melt spinning machine, a blend polymer was prepared by adding 8% by weight of PMP as Component B. Melt spinning was performed using a base of 08 mm, a slit diameter of 1.00 mmφ, and a 4 slit, and the other was obtained under the same spinning conditions as in the reference example to obtain a polyester composite multifilament fiber having a round cross section of 290 dtex-24 filament. . No yarn breakage occurred during spinning, and the yarn making property was excellent.

Using the fiber obtained by spinning, stretching was performed at a magnification of 3.5 times in the same manner as in the reference example. Although the yarn breakage occurred 6.7 times during the drawing, the drawing property was good. In addition, voids were observed at the interface between component A (polyester) and component B (PMP). The results of Reference Example 2 are shown in Table 2.

Comparative Example 1
In Reference Example 1, when melt spinning using a blend polymer of PET and PMP (8% by weight of PMP), melt spinning was performed in the same manner as in Reference Example 1 except that a round hole die was used, and 308 dtex. A polyester multifilament fiber having a round cross section of -24 filaments was obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

Using the fiber obtained by spinning, stretching was performed at a magnification of 3.5 times in the same manner as in the reference example. Although the yarn breakage occurred 3.2 times during drawing, the drawability was good. The results of Comparative Example 1 are shown in Table 2. Compared with the reference example 1, although the space | gap was seen in the interface of the component A and the component B, it turned out that specific gravity is large and it is inferior to lightweight property by not forming a hollow part.

Comparative Example 2
Without using the component B (PMP) in Reference Example 1, the PET monocomponent except for using as the sea component of the sea-island composite spinning using hot water soluble PET to the island component in the same manner as in Reference Example 1, island 4 The sea-island composite spinning was carried out to obtain a polyester multifilament fiber having a round cross section of 290 dtex-24 filaments. No yarn breakage occurred during spinning, and the yarn making property was excellent.

Using the fiber obtained by spinning, stretching was performed at a magnification of 3.5 times in the same manner as in the reference example. During drawing, breakage of the yarn or winding of a single yarn around the roller occurred and the drawability was poor. The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. The results of Comparative Example 2 are shown in Table 2. Compared with Reference Example 1, it was found that the lightness was poor because no voids were formed.

Reference example 3
When melt spinning using a polyester obtained in the Reference Example using a twin-screw extruder type melt spinning machine, 8% by weight of PMP as component B, ethylene terephthalate and poly (ethylene oxide) glycol as compatibilizers [ A blend polymer was prepared by adding 200% by weight of a copolymer with a molecular weight of 4000] (hereinafter referred to as PET-PEG; 10% copolymerized poly (ethylene oxide) glycol component) to the amount of PMP added. A polyester composite multifilament fiber having a round cross section of 301 dtex-24 filaments was obtained by the same spinning method as in Reference Example 1 except that the one was used as a sea component in composite spinning. No yarn breakage occurred during spinning, and the yarn making property was excellent.

Using the fiber obtained by spinning, stretching was performed in the same manner as in Reference Example 1. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. The results of Reference Example 3 are shown in Table 2. There are voids at the interface between component A and component B, and the PMP is more uniformly dispersed by using a compatibilizing agent, so that the porosity is higher than in Reference Example 1, resulting in a lower specific gravity. Also, the stretchability was excellent.

Reference example 4
When performing melt spinning using a polyester obtained in the Reference Example using a twin-screw extruder type melt spinning machine, a polypropylene (grade J108M, hereinafter abbreviated as PP) 5 manufactured by Grand Polymer Co., Ltd. was used as Component B. Weight%, PET-PEG as a compatibilizer, 320% by weight with respect to the amount of PMP added, blend polymers made to use as sea components in composite spinning, and hot water-soluble PET combined spinning The sea-island composite spinning is performed so that the sea: island = 70: 30 and the number of islands is 12. Otherwise, the cross-sectional shape of the 299 dtex-24 filament is round under the same spinning conditions as in the reference example. A polyester composite multifilament fiber was obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 3.5 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. In addition, voids were observed at the interface between component A and component B (PP). The results of Reference Example 4 are shown in Table 2.

Reference Example 5
In Reference Example 2, 10% by weight of polyethylene (Hizex, grade 8200B, hereinafter abbreviated as PE) manufactured by Mitsui Chemical Co., Ltd. as component B, and styrene copolymer of styrene copolymer (manufactured by Nippon Steel Chemical Co., Ltd.) MS200 (hereinafter abbreviated as “Estyrene”) was added to each PE in an amount of 10% by weight with respect to the added amount of PE, and a blend polymer was prepared. The slit width shown in FIG. Using a 00mmφ, T-shaped 4-slit die, melt spinning was performed in the same manner as in Reference Example 2, and then stretched at a magnification of 3.5 times in the same manner as in Reference Example. A fiber having During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent. In addition, voids were observed at the interface between component A and component B (PE). The results of Reference Example 5 are shown in Table 2.

Reference Example 6
In Reference Example 3, nylon 6 amylan (registered trademark, type CM1017) manufactured by Toray Industries, Inc. was used as component A after drying at 133 Pa for 24 hours, PMP was used as component B, and Toray DuPont Co., Ltd. was used as a compatibilizer. ) Made of Hytrel (type 4057, hereinafter abbreviated as Hytrel) to component B by adding 20% by weight of each blend polymer was used as a sea component in composite spinning, and hot water-soluble PET was used as composite spinning. The sea-island composite spinning was performed so that the sea: island = 65: 35 and the number of islands was 12, and the other 299 dtex-24 filament had a round cross section under the same spinning conditions as in the reference example. A polyester composite multifilament fiber was obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 3.5 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Gaps were observed at the interface between component A (nylon 6) and component B (PMP). The results of Reference Example 6 are shown in Table 2.

Reference Examples 7-10
When performing melt spinning using a biaxial extruder type melt spinning machine using the polyester obtained in the Reference Example, the addition amount was variously changed as shown in Table 3 using PMP as component B, and a compatibilizing agent As a sea component in composite spinning, a blend polymer prepared by using styrene as an addition amount for component B as shown in Table 3 is used as a sea component in composite spinning. The sea-island composite spinning was carried out so that the number of islands was 32, and the polyester composite multifilament fiber having a round cross section of 299 dtex-36 filaments was obtained under the same spinning conditions as in the reference example. . No yarn breakage occurred during spinning, and the yarn making property was excellent.

In the same manner as in the reference example, the fiber obtained by spinning was stretched at a magnification of 3.5 times for Reference Examples 7 and 9, and at a magnification of 3.0 times for Reference Examples 8 and 10. In Reference Example 8, single yarn winding occurred 3.2 times during drawing, but at other levels, yarn breakage or single yarn winding on the roller did not occur during drawing, and the drawability was generally excellent. .

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Each result is shown in Table 3. In all of Reference Examples 7 to 10, voids were observed at the interface between Component A and Component B. As a result, it was found that Reference Examples 9 and 10 were superior to Reference Examples 7 and 8 in terms of lightness and stretchability, and that by optimizing the addition amount of Component B, the yarn physical properties and yarn forming properties were more excellent.

Reference Examples 11-14
When melt spinning using a biaxial extruder type melt spinning machine using the polyester obtained in the Reference Example, PP is used as Component B and the addition amount is 5% by weight as shown in Table 3, and compatibilization is performed. A blend polymer prepared by variously changing the amount added to Component B using PET-PEG as an agent as shown in Table 3 is used as a sea component in composite spinning, and hot water-soluble PET is used as an island component in composite spinning. Used, sea-island composite spinning is performed so that sea: islands = 45: 55 and the number of islands is 144, and the others are the same spinning conditions as in the reference example, and the 302 dtex-12 filament has a round cross-sectional shape. Filament fibers were obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

In the same manner as in the reference example, the fibers obtained by spinning were stretched at a magnification of 3.2 for Reference Examples 11 and 13 and at a magnification of 3.5 for Reference Examples 12 and 14. In Reference Examples 11 and 12, a single yarn was wound twice or three times during drawing, but at other levels, no yarn breakage or single yarn winding on the roller occurred during drawing, and the drawability was generally excellent. It was.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Each result is shown in Table 3. In all of Reference Examples 11 to 14, voids are observed at the interface between Component A and Component B. As a result, Reference Examples 13 and 14 are superior to Reference Examples 11 and 12 in terms of lightness and stretchability, and are compatibilizers. It was found that by optimizing the amount of added, the properties of the yarn and the yarn-making property were more excellent.

Reference Example 15
When performing melt spinning similar to Reference Example 4, PE of Reference Example 5 was used as Component A, and Ipiace (registered trademark, type AH90, glass transition temperature 172 ° C., manufactured by Mitsubishi Engineering Plastics Co., Ltd.) The cross-sectional shape of the 217 dtex-24 filament was the same as in Reference Example 4 except that the blended polymer prepared by adding 10% by weight of PPE was used as the sea component in composite spinning and the spinning temperature was 300 ° C. A round composite multifilament fiber was obtained. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  The fiber obtained by spinning was stretched at a magnification of 4.0 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. It was found that voids were observed at the interface between component A (PE) and component B (PPE) .

Example 16
When performing melt spinning similar to Reference Example 4, the polyester obtained in the Reference Example as Component A and Norbornene resin Arton (registered trademark, type F5023 , glass transition temperature 166 ° C. ) manufactured by JSR Co., Ltd. as Component B 10% by weight of each was added as a blend polymer to obtain a composite multifilament fiber having a round cross-sectional shape of 310 dtex-24 filament in the same manner as in Reference Example 4, using the sea component in composite spinning. . No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 5.5 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Voids were observed in the interface of the components A and B.

Example 17
When performing melt spinning similar to Reference Example 4, as component A, nylon 6 amylan (registered trademark, type CM1017 , glass transition temperature 40 ° C. ) manufactured by Toray Industries, Inc. was used after being dried at 133 Pa or less for 24 hours. As component B, 10% by weight of Apel (registered trademark, type 6015T, glass transition temperature 142 ° C.) manufactured by Mitsui Chemical Co., Ltd. was added to prepare a blend polymer as a sea component in composite spinning. A composite multifilament fiber having a round cross section of 241 dtex-24 filaments was obtained in the same manner as in Reference Example 4 except that the temperature was changed to 0 ° C. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  The fiber obtained by spinning was stretched at a magnification of 4.0 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Voids were observed in the interface of the components A and B.

Reference Example 18
When performing melt spinning similar to Reference Example 4, the polyester obtained in the Reference Example was used as Component A, and 10% by weight of PPE of Reference Example 15 was added as Component B to prepare a blend polymer. Was used as a sea component in composite spinning, and a composite multifilament fiber having a round cross section of 302 dtex-24 filament was obtained in the same manner as in Reference Example 4 except that the spinning temperature was 290 ° C. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 5.0 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Voids were observed in the interface of the components A and B.

Example 19
When performing melt spinning similar to Reference Example 4, the polyester obtained in the Reference Example was used as Component A, and ZEONOR manufactured by Nippon Zeon Co., Ltd. (registered trademark, type 1600R, glass transition temperature 163 ° C., below) The blend polymer was prepared by adding 5% by weight of ZEONOR) and 20% by weight of Hytrel of Reference Example 6 as a compatibilizing agent to the amount of ZEONOR, and used as a sea component in composite spinning. A composite multifilament fiber having a round sectional shape of 283 dtex-24 filaments was obtained in the same manner as in Reference Example 4 except that. No yarn breakage occurred during spinning, and the yarn making property was excellent.

  Using the fiber obtained by spinning, stretching was performed at a magnification of 5.5 times in the same manner as in the reference example. During drawing, breakage of the yarn and winding of a single yarn around the roller did not occur, and the drawability was excellent.

The fiber obtained by stretching was immersed in hot water to remove the copolymer PET on the island, and then a hollow blend fiber was obtained. Voids were observed in the interface of the components A and B.

Since the hollow blended fiber obtained by the present invention has a hollow portion in the fiber that communicates with the void in the fiber axis direction, it is very excellent in lightness. Also, in the fiber properties, since the fiber strength can be 3.5 cN / dtex or more, or the apparent specific gravity of the fiber can be 1.2 or less, it is used not only as a lightweight clothing for infants or the elderly, In addition to being used for sports uniforms and outdoor sports applications, it is also used for industrial materials such as automobile interiors, BCFs, and various transports such as automobiles, ships, airplanes, and railroads that are required to be lightened to save energy. It is also suitably used for such packing materials.

In this invention, it is a specific example of the nozzle | cap | die discharge hole which makes the fiber of a hollow round cross section. In this invention, it is a specific example of the hollow round cross section obtained using the nozzle | cap | die discharge hole of FIG. It has four hollow parts and countless voids.

Claims (9)

In a blended fiber composed of component A having fiber-forming ability and component B which is a thermoplastic polymer, the relationship between the critical surface tension γ _{cA of} component A and the critical surface tension γ _cB of component B is γ _cA −γ _cB ≧ 10 dyne / cm, the glass transition temperature (Tgb) of component B is 5 ° C. or higher and 130 ° C. or higher than the glass transition temperature (Tga) of component A, component A is sea, and component B is island A hollow blended fiber excellent in lightness, characterized in that it has a hollow portion at least part of the composite interface between component A and component B and communicated in the fiber axial direction. The hollow blend fiber excellent in lightweight property according to claim 1, wherein the content of component B in the hollow blend fiber is 1 to 40% by weight. The hollow blend fiber excellent in lightness according to claim 1 or 2, wherein component B has a critical surface tension γ _{cB of 10} to 30 dyne / cm. The hollow blend fiber excellent in lightweight property according to any one of claims 1 to 3, wherein the density of the component B is 1.0 g / cm ³ or less. The lightness according to any one of claims 1 to 4, comprising a compatibilizing agent, wherein the content of the compatibilizing agent is 2 to 500% by weight based on the content of component B. Excellent hollow blend fiber. The hollow blend fiber excellent in lightweight property according to any one of claims 1 to 5 , wherein the apparent specific gravity of the fiber is 1.2 or less. The hollow blend fiber excellent in lightweight property according to any one of claims 1 to 6 , wherein the fiber strength is 3.5 cN / dtex or more. The hollow blend fiber excellent in lightweight property according to any one of claims 1 to 7 , wherein Component A is a polyester polymer, a polyamide polymer, or a polyolefin polymer. A fiber product using the hollow blend fiber according to any one of claims 1 to 8 in part or in whole.

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