JP5454191B2 - Crimped yarn and fiber structure - Google Patents

Description

  The present invention relates to a crimped yarn made of polyamide 56, which is excellent in flexibility, stretchability, moisture absorption / release properties, and heat resistance. More specifically, the present invention relates to a crimped yarn excellent in abrasion resistance, mechanical properties, bulkiness and dyeing properties.

In general-purpose synthetic fibers, polyamide fibers are superior in wear resistance, flexibility and heat resistance in addition to high mechanical properties represented by strength.In addition to clothing, tire cords, airbags, ropes, nets, etc. It is suitably used for all material applications.
Among these, for clothing, its high flexibility, familiarity with the skin, and stretch back properties are evaluated, and it is mainly used for inner and pantyhose. In these applications, polyamide 66 is widely used in Europe and the United States, and polyamide 6 is widely used in the Asian region. Each polyamide has advantages and disadvantages. For example, polyamide 66 has advantages such as high heat resistance due to high melting point, excellent wear resistance, and fastness to dyeing, while low level dyeing due to slow dyeing speed, It has drawbacks such that gels and spherulites are likely to be produced during production, and defects tend to occur, and raw material costs are high. On the other hand, polyamide 6 can be produced at a relatively low cost, and since it is difficult to produce gels and spherulites, it can be easily produced in industrial production. Have. On the other hand, compared to polyamide 66, it has disadvantages such as poor abrasion resistance and heat resistance and low dyeing fastness. In addition, since any of the polyamides is not so hygroscopic, a method of blending highly hygroscopic materials (Patent Document 1) is industrially adopted in order to improve familiarity with the skin and maintain comfort. . However, when this method is used, the heat resistance, abrasion resistance and dyeing fastness of the fiber tend to decrease.

  By the way, recently, with increasing awareness of the environment on a global scale, non-petroleum-derived fiber materials are eagerly desired. The general-purpose polyamide fiber described above uses petroleum as a main raw material, and uses a large amount of water and heat energy at the time of production, and has a large amount of carbon dioxide emission. Therefore, it can be said that the material has a large environmental load. As pointed out in the peak oil theory (Non-Patent Document 1), the price of oil has risen with a decrease in petroleum resources, and global warming caused by mass consumption of petroleum resources has been taken up as a major problem. ing.

  Therefore, spotlight has been applied to non-petroleum-derived plastics (biomass plastics), and research and development are actively conducted in Europe, the United States, Japan, and China. For example, cellulose produced as a natural resource can be taken out in large quantities from plant resources that take up carbon dioxide from the atmosphere and grow, and contribute to the suppression of global warming through the circulation of carbon dioxide (carbon neutral). It is expected that. Typical examples of biomass plastics include aliphatic polyesters such as polylactic acid, but their properties such as strength, heat resistance, wear resistance, and hydrolysis resistance are low compared to general-purpose plastics. In order to use it, it is necessary to greatly improve these characteristics.

  Therefore, we are conducting research focusing on bionylon polymerized using biomass-based monomers to satisfy the mechanical properties, durability, and other properties that are sufficient as general-purpose materials. As bionylon, although polyamide 11, polyamide 12, and polyamide 610 have already been industrialized, all polyamides are biased in their characteristics, so they are used for clothing and industrial material applications in a very small part. Only. Therefore, we focused on polypentamethylene adipamide (polyamide 56) obtained by heat polymerization of 1,5-pentamethylenediamine, which is a biomass-based monomer, and adipic acid as a novel bionylon. Polyamide 56 is a novel material that has not been industrialized yet, but several patents have been published for manufacturing methods (Patent Documents 2 and 3).

  Further, a polyamide 56 (Non-patent Document 2) manufactured by heat polymerization has been known conventionally, but a polyamide 56 obtained by heat polymerization is a polyamide 56 (Non-patent Document 3, Only those having a lower melting point and inferior heat resistance have been reported as compared with Non-Patent Document 4). On the other hand, the interfacial polymerization method is not suitable industrially because it is a complicated process and is a high-cost manufacturing process. Therefore, as disclosed in Patent Document 2, high purity 1,5 pentamethylenediamine obtained by an enzyme reaction using lysine decarboxylase or the like, or using a specific polymerization method as described in Patent Document 3 is used. Thus, the polyamide 56 having a high melting point and a practical polymerization degree has been successfully produced by the heat polymerization method. The polyamide 56 has potential as a fiber material because it can be spun and drawn in addition to excellent melt storage stability.

  As the fiber material, for example, a filament made of polyamide 56 having excellent transparency and high strength is disclosed (Patent Document 4). In this patent document, a monofilament suitable for fishing line and the like is disclosed as a specific example, but in the examples, a monofilament having a diameter of 79 μm is obtained by reducing the draw ratio to such an extent that the yarn is not broken. That is, in the method of Patent Document 4, fibers having a fine fineness (usually 5 to 17 μm in diameter) mainly for clothing cannot be stably produced.

  Further, BCF (Bulked Continuous Filament) is disclosed as a crimped yarn made of polyamide 56 (Patent Documents 5 and 6). For example, paragraph (0031) of Patent Document 5 describes BCF in the range of 20 to 100 μm in terms of monofilament diameter, and therefore only describes thick fiber yarns as in Patent Document 4. Furthermore, since the production method of the BCF yarn is a crimped crimp, the fastness of crimping is low. For example, the crimp retention rate under restraint load described in the example of Patent Document 6 is 52% at the maximum, which indicates that the crimped yarn has a structure that is easy to loosen under a high load. Therefore, the BCF yarn cannot be used in applications where the shape does not change even when stretching and stretching of several thousand to several tens of thousands is repeated as in sports clothing.

  Further, a polyamide 56 fiber used for a rubber reinforcing cord, which is a fiber made of polyamide 56, is disclosed (Patent Document 7). However, the fiber of this patent document is a fiber having an extremely high modulus of elasticity of 12 to 20% after 4.68 cN / dtex stress after dry heat treatment at 150 ° C. for 30 minutes. That is, since it is a fiber that is hard to bend, it has insufficient flexibility and cannot be used as it is as a fiber for clothing.

JP-A-7-150414 (Claims) JP 2003-292612 A (Claims, [0045]) JP 2004-075932 A (Claims, [0034]) JP 2006-144163 A (Claims) JP 2007-84936 A (Claims, [0031]) JP 2009-179899 A (Claims) JP 2009-68132 A (Claims)

ASPO (The Association for the Study of Peak Oil) J. et al. Polym. Sci. 2,306 (1947) J. et al. Polym. Sci. 50, 87 (1961) Macromolecules, 30, 8540 (1998)

  An object of the present invention is to provide a crimped yarn excellent in flexibility, stretchability, moisture absorption / release properties, and excellent in heat resistance. More specifically, it is to provide a crimped yarn excellent in abrasion resistance, mechanical properties, bulkiness and dyeing properties.

  As a result of intensive studies by the present inventors to obtain a polyamide 56 crimped yarn excellent in flexibility, stretchability and moisture absorption and desorption, the relative viscosity of sulfuric acid is in a specific range, and the molecular weight distribution (Mw / Mn) is By forming a small polyamide 56 filament, the degree of orientation and crystallinity of the polyamide 56 molecular chain in the spinning process is sufficiently increased, and the polyamide 56 has excellent mechanical properties and heat shrinkage properties while having fineness and few fluff. Succeeded in producing filaments. The filament is excellent in false twisting workability, and cannot be achieved with conventional polyamide filaments by optimizing the draw ratio, false twist and tension, set temperature, and relaxation rate after drawing. High elasticity and flexibility can be imparted. Further, by moderately relaxing the degree of orientation of the amorphous molecular chains of the polyamide 56, the moisture absorption / release parameter ΔMR: succeeded in achieving 3% or more.

  That is, the present invention is a filament made of polyamide 56 having a relative viscosity of sulfuric acid of 2.0 to 3.5 and Mw / Mn of 1.5 to 3, and 5% elongation stress: 0.2 to 1.0 cN / It is achieved by a polyamide 56 crimped yarn characterized by dtex, boiling water shrinkage ratio: 1 to 15%, expansion / contraction recovery ratio: 10 to 55%, moisture absorption / release parameter ΔMR: 3% or more .

  The crimped yarn of the present invention is made of polyamide 56, and preferably made of polyamide 56 synthesized using a non-petroleum-derived monomer. In other words, it is an environmentally friendly material that emits less carbon dioxide. Moreover, since it is a crimped yarn excellent in flexibility, stretchability, moisture absorption and desorption, and excellent in heat resistance, it can be suitably used mainly for clothing applications. Furthermore, since it is excellent in strength and abrasion resistance, it is possible to provide a crimped yarn and a fiber structure that can be used for industrial materials.

1 is a schematic view of a spinning device preferably used in the present invention. It is the schematic of the false twist processing machine preferably used by this invention.

  The crimped yarn of the present invention needs to contain polyamide 56 in which 90 mol% or more of repeating units are composed of pentamethylene adipamide units. Here, the pentamethylene adipamide unit is a structural unit composed of 1,5-pentamethylenediamine and adipic acid. In the range not impairing the effects of the present invention, other copolymerization components of less than 10 mol% may be included. However, the higher the pentamethylene adipamide unit, the higher the regularity of the molecular chain, and the easier the orientation crystallization in the spinning process. Therefore, a crimped yarn excellent in strength, wear resistance, heat resistance, and stretchability is obtained, which is preferable.

  Further, the fiber structure comprising the crimped yarn of the present invention has a low molecular weight of the repeating unit as compared with hexamethylene adipamide (polyamide 66), that is, a large number of amide bonds per polymer unit weight. Familiarity with commonly used coating agents is extremely good. Therefore, it is possible to reduce the thickness of the coating agent used as the binder, and there is an advantage that it is difficult to obtain a rough texture that is often pointed out in the coating system. Accordingly, the pentamethylene adipamide unit is preferably higher, preferably 95 mol% or more, more preferably 97 mol% or more, and more preferably 99 mol% or more.

  The crimped yarn of the present invention needs to have a relative viscosity of sulfuric acid of 2.0 to 3.5, which is an index of molecular weight. By setting the relative viscosity of sulfuric acid, which indicates the molecular weight, to 2.0 or more, the molecular orientation during spinning becomes good, and the strength and wear resistance applicable to general-purpose clothing materials are exhibited. Furthermore, by setting the spinning speed to 4000 m / min or higher, orientation crystallization progresses significantly without performing a drawing operation, and there is little occurrence of yarn breakage or fluffing in the subsequent false twisting process. A filament excellent in properties can be obtained. In addition, by making the relative viscosity of sulfuric acid 3.5 or less, stable operation at a high speed exceeding the spinning speed of 7000 m / min becomes possible, and filaments with extremely small strength, thickness in the length direction, and molecular orientation spots can be obtained. Can be obtained. In addition, the higher the sulfuric acid relative viscosity, the better the strength and abrasion resistance. However, in consideration of spinning operation, yarn homogeneity, and dyeability, the sulfuric acid relative viscosity is preferably 2.4 to 3.1. 2.6 to 2.9 is more preferable.

  Furthermore, it is extremely important that the crimped yarn of the present invention has a narrow molecular weight distribution. The molecular weight distribution can be simply represented by the degree of dispersion (Mw / Mn), which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn. The smaller this value, the narrower the molecular weight distribution. This molecular weight distribution can be achieved by carrying out strict polymerization such as the purity of the monomer used during polymerization, the presence or absence of specific impurities, the amount charged during polymerization, the polymerization temperature and time, and the like. Details of the polymerization method will be described later. Also, in the spinning process, the molecular weight distribution fluctuates in an increasing direction, so that it is necessary to optimize spinning conditions.

  The crimped yarn of the present invention needs to have a dispersity (Mw / Mn) of 1.5 to 3. The lower the degree of dispersion (Mw / Mn), the better the strength, the smaller the warp in the longitudinal direction of the yarn, and the smaller the internal structure of the fiber (the amount of crystal and amorphous and the degree of orientation). High crimped yarn. The reason why such a highly homogenous fiber can be obtained is that the degree of dispersion and the interaction force (the number of molecular chains interacting with each other by reducing the distribution of molecular chain length, that is, the interaction force ( (The physical entanglement force, hydrogen bonding force, van der Waals force, etc.) become smaller, and each molecular chain is evenly tensioned during the yarn-making process, so the amorphous molecular chains are uniformly oriented to form crystals. Is also considered to be stable. In particular, polyamide 56 is relatively loose in amorphous phase and has a large number of amide bonds per unit weight, so it absorbs moisture and is easily affected by water. Is difficult. Therefore, a molecular weight distribution with a low degree of dispersion is a very important parameter for improving the quality of crimped yarn. Mw / Mn is preferably 2.7 or less, and more preferably 2.4 or less. More preferably, it is 2.2 or less. In our study, 1.5 is close to the manufacturing limit.

  The crimped yarn of the present invention needs to have a 5% elongation stress of 0.2 to 1.0 cN / dex. The 5% elongation stress has a correlation with the bending rigidity of the fiber, and the smaller this value, the easier the fiber bends. That is, the fabric has excellent flexibility. Further, since the elongation stress is low, generation of fluff in the product manufacturing process and the product is suppressed, and the product is extremely excellent in durability. When the 5% elongation stress is 1.0 cN / dtex or less, a flexible fabric having excellent bending recovery and durability can be obtained, preferably 0.8 cN / dtex or less, more preferably 0.5 cN / dtex or less. The elongation stress is at a level where the vicinity of 0.2 cN / dtex is close to the production limit.

  The crimped yarn of the present invention needs to have a boiling water shrinkage of 1 to 15%. Boiling water shrinkage is an extremely important parameter in fabric design. By setting this value to 15% or less, it becomes easy to obtain a fabric that is flexible and excellent in surface smoothness. Further, when the shrinkage rate is low, it is preferable that the structure of the amorphous phase hardly changes even when the crimped yarn is subjected to boiling water treatment in the dyeing process, and the dyeing solution is uniformly exhausted into the fiber and the leveling property is improved. . More preferably, it is 1-12%, More preferably, it is 1-10%, Most preferably, it is 1-8%.

  The crimped yarn of the present invention needs to have a stretch recovery rate (CR) of 10 to 55% based on a measurement method described later. By using a crimped yarn having a CR of 10% or more, it is possible to obtain a product having high stretchability, bulkiness, flexibility, and heat retention when formed into a fiber structure. On the other hand, if the CR exceeds 55%, the fabric has a feeling of wiping when it is made into a fiber structure, and the surface quality tends to deteriorate. Accordingly, CR is preferably 15 to 50%, more preferably 20 to 45%, in order to impart stretchability and bulkiness as a processed yarn while providing a high-quality fabric surface.

  In addition, in the clothes, the humidity tends to be higher than the outside air due to sweat or the like released from the external surface. The clothes are kept at a certain temperature and humidity, that is, by providing an air conditioning function, high comfort is exhibited. In recent years, there is a tendency to provide comfort materials by combining multiple materials with high hygroscopicity, materials with high surface smoothness, and materials with excellent stretch properties, but these composite materials are complicated to manufacture and increase costs In addition to this, it will also have many drawbacks due to the use of multiple materials. On the other hand, this material can provide a plurality of functions with a single material. In other words, the moisture absorption / desorption parameter ΔMR, which is one index of the air conditioning function, is 3% or more and exhibits high moisture absorption / release properties similar to cotton, and also has stretchability, flexibility, and high durability that exceed conventional nylon yarns. Is. The moisture absorption / release parameter ΔMR can also be controlled to some extent by controlling the molecular structure of the amorphous part. In the present invention, ΔMR is preferably 3.5% or more, more preferably 4.0% or more.

  Further, the crimped yarn of the present invention preferably has a 10% elongation recovery rate described later of 80% or more. The elongation recovery rate is the value when the yarn is fixed (original length) under a load of 0.18 cN / dtex so that the crimp of the crimped yarn is almost stretched, and is stretched and recovered by 10% from this state. It indicates the recovery rate, and it can be said that the higher this value is, the more difficult the crimp is to loosen and the higher the fastness of crimp. The 10% elongation recovery rate is more preferably 82% or more, and still more preferably 85% or more.

  The crimped yarn of the present invention preferably has an amino end group concentration of 25 to 80 eq / ton. If the amino terminal group concentration is 25 eq / ton or more, good dyeing property is exhibited at the time of dyeing, and if it is 80 eq / ton or less, it has good melt heat resistance, and it is difficult to yellow in the product. In particular, since the polyamide 56 is highly hygroscopic and easily affected by water, it is necessary to manage the amino terminal group concentration more severely than the general-purpose polyamide 6 and polyamide 66. A more preferred amino end group concentration is 30 to 70 eq / ton, and even more preferably 35 to 60 eq / ton. The reason why the dyeing property is improved is considered to be that the pentamethylene adipamide unit is a molecular structural unit that facilitates the bonding between the dye and the amino terminal group. That is, since the pentamethylene adipamide unit is a structural unit containing a large number of amide bonds per unit weight, the molecular weight of the repeating unit is smaller than that of the hexamethylene adipamide unit contained in polyamide 66 and the like, and the hydrophilicity is high. The crimped yarn easily exhausts and / or supports the dye liquid macroscopically, and the bond between the dye and the amino terminal group is promoted. Further, from the viewpoint of a microscopic molecular structure, the former has fewer carbon atoms in the diamine in the pentamethylene adipamide unit and the hexamethylene adipamide unit. Therefore, when the pentamethylene adipamide unit constitutes the amino terminal, the amino terminal group and the amide bond are in a closer positional relationship, and the dyeing solution is easily transported to the amino terminal group, increasing the reaction efficiency between the dye and the amino terminal group. Estimated.

As described above, the dyeing characteristics of the polyamide 56 crimped yarn include not only the concentration of amino end groups, but also the hydrophilicity and regularity of the repeating unit of the molecular chain, the crystal of the molecular chain inside the crimped yarn, the amorphous structure, etc. It is influenced by various structural units from the primary structure to the higher order structure of the polymer, and the crimped yarn contains many pentamethylene adipamide units, and the amino terminal group concentration and the carboxyl terminal group concentration described later It is expressed synergistically by controlling the balance and orientation crystallization structure. The amino end group concentration and the carboxyl end group concentration are preferable because the heat resistance of the fiber is improved and good dyeing property and dyeing fastness are exhibited by satisfying the following relationship.
0.5 ≦ [NH ₂ ] / [COOH] ≦ 2.0
[NH ₂ ]: Amino end group concentration of crimped yarn (eq / ton)
[COOH]: Carboxyl end group concentration of crimped yarn (eq / ton)
The balance ([NH ₂ ] / [COOH]) of the amino end group concentration and the carboxyl end group concentration is more preferably 0.7 to 1.6, and still more preferably 0.9 to 1.2. Most preferred is 0.95 to 1.05. The amino terminal group and the carboxyl terminal group are considered to be sites having high molecular mobility, and the molecular motion of the terminal group affects the mobility of the molecular chain skeleton existing in the amorphous phase. In the case of polyamide 56, the mobility of each terminal group is considered to be different from the characteristic that the diamine unit and the dicarboxylic acid unit have different carbon numbers. The amide bond is constrained by forming a hydrogen bond with an adjacent molecular chain, and the mobility is likely to decrease. It can be said that the greater the number of carbon atoms from the amide bond, the higher the degree of freedom of movement. Therefore, in the case of the polyamide 56, it is considered that the carboxyl end group has higher mobility than the amino end group. In order to obtain a crimped yarn excellent in dyeing fastness, it is important that the molecular motion of the amorphous phase is moderately restrained. Therefore, it is preferable that the concentration of both terminal groups be in a specific range.

  The crimped yarn of the present invention is mainly targeted for clothing, and the total fineness is preferably 10 to 550 dtex. When the total fineness is 550 dtex or less, even a thick fabric is a highly flexible fabric. On the other hand, since the total fineness is 10 dtex or more, a fabric having practical durability can be obtained even in extremely thin ground. More preferably, it is 20-440 dtex, More preferably, it is 30-330 dtex.

  The crimped yarn of the present invention preferably has a single fiber fineness of 0.01 to 5 dtex. When the single fiber fineness is 5 dtex or less, the bending rigidity of the single fiber is lowered, so that the bending rigidity of the crimped yarn is reduced and the flexibility of the fabric is increased. In addition, the lower the single fiber fineness, the greater the specific surface area of the fibers, so that the binding force between the crimped yarns constituting the woven structure increases, and the fabric is less likely to be misaligned by external forces (tensile force, frictional force, impact force, etc.) Become. On the other hand, the greater the single fiber fineness, the better the stretchability, so the single fiber fineness is more preferably 0.1 to 4 dtex, and even more preferably 0.5 to 3 dtex, from the balance between the flexibility and stretchability of the fabric. . In addition, what is necessary is just to select the number of filaments of the crimped yarn of this invention according to the objective and a use in the range used as said total fineness and single fiber fineness, However, It is preferable that it is the range of 3-2000.

  The crimped yarn of the present invention preferably has a strength of 4 cN / dtex. If the strength is 4 cN / dtex or more, a woven or knitted fabric having no practical problem can be obtained. More preferable strength is 5 cN / dtex or more, and further preferably 6 cN / dtex or more. The higher the strength, the better, but 12 cN / dtex is the limit even if the film is stretched extremely high. In addition, since the durability of the fabric, particularly the occurrence of fluff when using the product, can be suppressed when the residual elongation is high, the preferable residual elongation is 20 to 70%, and the more preferable residual elongation is 30 to 60%. A more preferable residual elongation is 40 to 50%.

The crimped yarn of the present invention preferably has a high melting point that serves as an index of heat resistance. The melting point is preferably 240 ° C. or higher, and more preferably 250 ° C. or higher. Also, the heat of fusion, which is an index of the amount of heat required for melting the fiber, is preferably high, preferably 50 J / g or more, and more preferably 60 J / g or more. Since the melting point and the heat of fusion are high, for example, excellent heat resistance can be exhibited even at work sites exposed to high temperatures, and melting and perforation can be suppressed. In addition, the said melting | fusing point refers to the peak temperature of the crystal melting in DSC mentioned later.
The smaller the yarn unevenness of the crimped yarn of the present invention, the smaller the variation in warp tension and weft tension in the warping process and weaving process, and the finished product can be finished into a high-quality product without dyeing spots. . For this reason, 0.1% to 3% is preferable for U% (normal mode), which is an index of yarn unevenness, more preferably 0.1 to 2%, and particularly preferably 0.1 to 1%.

  The crimped yarn of the present invention may be subjected to an entanglement treatment as required, and the CF value (Coherence Factor) can be selected within a range of 3 to 200.

  In the crimped yarn of the present invention, the cross-sectional shape of a single fiber can take a wide variety of cross-sectional shapes such as a round shape, a Y shape, a multileaf shape, a polygonal shape, a flat shape, a hollow shape, and a rice field shape. A round shape or a flat shape is preferred, and a round shape is most preferred in that a fabric with higher strength and lower air permeability can be obtained stably. Moreover, although the cross-sectional shape of each single fiber may be the same or different, it is preferable that it is the same.

  The crimped yarn of the present invention may be a long fiber or a short fiber cut to an appropriate length. The crimped yarn of the present invention refers to a generally known false twisted yarn, which is a fiber having bulkiness and stretchability due to the bending or spiral structure of a single fiber.

  The crimped yarn of the present invention is a composite yarn in a single fiber such as a core-sheath composite yarn (single core, multi-core, core component partial exposure), bimetal composite yarn, etc., within the range not impairing the object effect of the present invention, Although it may be an alloy fiber alloyed with another polymer, it is preferably a crimped yarn containing a single component of polyamide 56 in terms of a crimped yarn having higher strength. Examples of other polymers that can be combined and alloyed are shown below.

  For example, polyester (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid, etc.), polyamide (polyamide m such as polyamide 6 having a repeating unit of 4 to 12 carbon atoms, polyamide 66, etc. and having a repeating unit having 4 to 12 carbon atoms and 4 to 12 carbon atoms, polycarbonate, polystyrene, polypropylene, polyethylene, polyoxymethylene, polymethyl methacrylate, polyethylene glycol, etc. Homopolymers and copolymer polymers (the above-mentioned polymers including the components exemplified below as copolymerization components) can be appropriately selected.

  The crimped yarn of the present invention can also be used after being mixed with other fibers, blended, blended, etc. For example, other fibers include natural fibers such as cotton, hemp, wool, silk, and rayon. Recycled fibers such as cupra, semi-synthetic fibers such as acetate, and polyamides (polyamide m such as polyamide 6 having a carbon number m of 4 to 12 and polyamide mn such as polyamide 66 and repeating units. Having 4 to 12 carbon atoms and 4 to 12 carbon atoms), polyester (polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, etc.), polyacrylonitrile, polypropylene, polyvinyl chloride, etc. Synthetic fibers containing homopolymers and copolymerized polymers (the above polymers including the components exemplified below as copolymerization components) That.

  Further, the crimped yarn of the present invention includes, for example, antioxidants and heat stabilizers (hindered phenol compounds, hydroquinone compounds, thiazole compounds, phosphorus compounds such as phenylphosphonic acid, and imidazoles such as 2-mercaptobenzimidazole. Compounds, substituted compounds thereof, copper halides, iodine compounds, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.) ), Gloss improver (titanium oxide, calcium carbonate, etc.), dye (nigrosine, aniline black, etc.), crystal nucleating agent (talc, silica, kaolin, clay, etc.), plasticizer (octyl p-oxybenzoate, N-butyl) Benzenesulfonamide), antistatic agent (a) Killsulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (melamine) Cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin or these brominated flame retardants and antimony trioxide A small amount of combination etc.).

The polyamide 56 of the present invention may be one in which other compounds are copolymerized in addition to 1,5-pentamethylenediamine and adipic acid as long as the object of the present invention is not impaired. A structural unit derived from may be included.
For example, aliphatic carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, octadecane Diacids), alicyclic dicarboxylic acids (cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxy Ethanedicarboxylic acid, diphenylethanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, etc.) Can.

Further, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diamino Such as octadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, aliphatic diamine such as 2-methyl-1,5-pentamethylenediamine, cyclohexanediamine, bis- (4-aminohexyl) methane Aromatic diamines such as alicyclic diamine and xylylenediamine It may include structural units derived from the like.
Examples of the diol compound include ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, hydroquinone, resorcin, dihydroxybiphenyl, naphthalenediol, anthracenediol, phenanthrenediol, 2, Structural units derived from aromatic, aliphatic, and alicyclic diol compounds such as 2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, and bisphenol S can be included.

  In addition, a hydroxycarboxylic acid having a hydroxyl group and a carboxylic acid as one compound is also exemplified. For example, lactic acid, 3-hydroxypropionate, 3-hydroxybutyrate, 3-hydroxybutyrate valerate, hydroxybenzoic acid, hydroxynaphthoate. Structural units derived from aromatic, aliphatic and alicyclic hydroxycarboxylic acids such as acids, hydroxyanthracene carboxylic acids, hydroxyphenanthrene carboxylic acids and (hydroxyphenyl) vinyl carboxylic acids can be included.

  In addition, structural units derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam can be included.

  The crimped yarn of the present invention has excellent mechanical properties, heat resistance, wear resistance and bulkiness, flexibility, and stretchability while having a small total fineness and single fiber fineness, and is therefore used as a wide variety of fiber structures. be able to. For example, it can be a fabric (woven fabric, knitted fabric, non-woven fabric, pile fabric, etc.) or a string-like product (rope, tape, braid, etc.), and is particularly widely used for clothing. For example, outerwear and innerwear such as outdoor wear, sportswear, golf wear, athletic wear, blouson, shirts, uniforms, pants, etc. and innerwear such as cups and pads, pantyhose, tights, For leg use such as socks. Also, comforters, mattresses, skin comforters, kotatsu futons, cushions, baby futons, blankets, pillows, cushions and other linings, covers, mattresses and bed pads, hospital, medical, hotel and baby use It can also be preferably used for bedding materials that touch human skin, such as sheets, and sleeping bags, cradle, and covers for baby strollers. The fiber structure may contain fibers other than the polyamide 56 crimped yarn, but in order to take advantage of the excellent properties of the polyamide 56 crimped yarn of the present invention, 50% by weight or more of the polyamide 56 crimped yarn of the present invention is used. It is preferable that the yarn is contained, more preferably 70% by weight or more, and further preferably 90% by weight or more.

  The crimped yarn of the present invention has an appropriate boiling yield in addition to the above-mentioned characteristics, and has high strength and low elastic modulus after boiling water treatment. It is possible to obtain a fiber structure having high density and high flexibility. Taking advantage of such features, for example, the crimped yarn of the present invention is warped, woven into a woven fabric, and then thermally contracted by heat treatment such as refining and final set, so that flexibility, bulkiness, stretchability, mechanical properties, A high-density fabric excellent in heat resistance and durability can be obtained.

  The crimped yarns of the present invention are classified into a monomer synthesis step, a polymerization step, a third spinning step (spinning step, drawing step), and a fourth crimping step, respectively, in the production process. It is preferable to employ a specific manufacturing method in this step. In order to achieve an amino end group concentration of 25 to 80 eq / ton, which is a constituent requirement of the crimped yarn of the present invention, a production method in the polymerization step is particularly important. Hereinafter, preferred embodiments will be described in order from the monomer synthesis step.

  Here, in the monomer synthesis step, 1,5-pentamethylenediamine is preferably synthesized from a biomass-derived compound such as glucose or lysine by an enzyme reaction, a yeast reaction, a fermentation reaction, or the like. According to the above method, since the content of a compound such as 2,3,4,5-tetrahydropyridine and piperidine is small and high-purity 1,5-pentamethylenediamine can be prepared, polyamide 56 having high melt storage stability is obtained. Since it becomes a resin, a decrease in molecular weight in the melt spinning process is suppressed, and the change in Mw / Mn is small, which is preferable. Moreover, since it is a material derived from biomass, there is also a merit that it is excellent in environmental adaptability. Specifically, JP 2002-223771 A, JP 2004-000114 A, JP 2004-208646 A, JP 2004-290091 A, JP 2004-298034 A, JP 2002-2002 A, and the like. 1,5-pentamethylenediamine, or 1,5-pentanediamine / hydrochloride, 1,5-pentamethylenediamine / adipate disclosed in JP-A No. 223770, JP-A-2004-2222569, etc. Polymerized polyamide 56 is preferable, and it is preferable to perform polymerization using 1,5-pentamethylenediamine adipate because it is easy to obtain a raw material with higher purity. Moreover, what is necessary is just to use what was manufactured by the conventionally well-known method about adipic acid, another diamine component, and a dicarboxylic acid component.

In addition, ASTM D6866 based on the principle of C14 (radiocarbon) dating is used as a method for determining whether the crimped yarn of the present invention and the fiber structure containing it are synthesized from a biomass-derived compound. is there. Specifically, after the sample (polymer) is dried to remove moisture, the sample is weighed, and CO ₂ generated by burning the sample is adsorbed to the adsorbent through a chemical operation, and measured with a liquid scintillation counter. method, after the CO ₂ generated by burning the carbon graphite, a method of measuring by accelerator mass spectrometry, a method that benzene from CO ₂ generated by burning synthesized, measured by a liquid scintillation counter, a sample such as by The concentration of the biomass ratio in it can be specified.

  Next, the polymerization method of the polyamide 56 resin used for the crimped yarn of the present invention will be described. As a method for polymerizing polyamide, a heat polymerization method and an interfacial polymerization method are known, but it is preferable to produce them by a heat polymerization method. Processes such as the interfacial polymerization method are complicated, and it is extremely difficult to realize an industrial manufacturing process. The heat polymerization method of the present invention is a polymerization method for obtaining a polyamide 56 resin by heating an aqueous solution containing diamine and adipic acid as raw materials to cause dehydration condensation.

  And as a preferable example of the heating polymerization method of the present invention, a raw material adjustment step (preparing an aqueous solution containing the raw material and putting it in a polymerization can), a concentration step (heating while maintaining the polymerization system in a slightly pressurized state, Volatilizes water in the aqueous solution to concentrate the raw material), pressurization step (the inside of the polymerization system is a closed system, and the aqueous solution containing the raw material is heated to generate water vapor, thereby increasing the pressure to the desired pressure in the pressure control step) And a pressure controlling step (heating while maintaining the inside of the polymerization system at a constant pressure to produce a prepolymer), and a pressure releasing step (releasing the pressure and returning to normal pressure) And a pressure reducing step (heating above the melting point of the produced polymer and maintaining the pressure under reduced pressure to advance polycondensation), and a discharging step (injecting an inert gas into the polymerization can to produce the produced polymer). Discharge).

  As a result of investigations by the present inventors, it has been found that it is difficult to obtain a polyamide 56 resin having a high amino terminal group concentration by a conventionally known heat polymerization method. As one of the causes, 1,5-pentamethylenediamine (boiling point: 180 ° C.) which is a raw material of polyamide 56 resin is different from 1,6-hexamethylenediamine (boiling point 200 ° C.) which is a raw material of conventional polyamide 66. Compared to this, the boiling point is low, and it is easy to volatilize at the temperature of the heat polymerization, so that the molar balance of amino terminal groups and carboxyl terminal groups in the polymerization can easily be lost in the latter stage of polymerization, and a polyamide 56 resin having a high amino terminal group can be obtained. Is difficult.

  Therefore, when 1,5-pentamethylenediamine is charged excessively with respect to adipic acid at the start of polymerization to supplement 1,5-pentamethylenediamine that volatilizes by heating polymerization, and the temperature reached, the polymerization time, etc. are specified. However, it was found that it was difficult to adjust the amino end group concentration only with these formulations.

  Therefore, as a result of intensive investigations on a method for suppressing the volatilization of 1,5-pentamethylenediamine, the cause of volatilization is that 1,5-pentamethylenediamine has a low boiling point and the hydrophilicity of 1,5-pentamethylenediamine is high. Therefore, it was found that 1,5-pentamethylenediamine is likely to volatilize with the evaporation of water. For this reason, it was found that when the aqueous solution was heated to a high temperature from the initial stage of polymerization where the polymerization reaction hardly proceeded, 1,5-pentamethylenediamine easily volatilized with the evaporation of water. Specifically, when the liquid temperature exceeds 150 ° C. from the initial stage of polymerization, volatilization of 1,5-pentamethylenediamine tends to be promoted.

  Therefore, the concentration of the aqueous solution in the raw material adjustment step is adjusted to 55 to 85% by weight, the temperature of the aqueous solution in the concentration step is set to 100 to 150 ° C., the concentration of the aqueous solution is concentrated to 80 to 95% by weight, and then the pressure increasing step is performed. Thus, by producing the polyamide 56 resin, volatilization of 1,5-pentamethylenediamine in the polymerization process can be suppressed, and the amino end group concentration can be controlled.

By setting the concentration of the aqueous solution in the raw material adjustment step to 55% by weight or more, water evaporated in the subsequent concentration step is reduced, and the volatilization amount of 1,5-pentamethylenediamine can be reduced. Here, the concentration of the aqueous solution is a value obtained by dividing the total weight of the raw material monomers by the weight of the aqueous solution and multiplying by 100. On the other hand, by setting it to 85% by weight or less, the temperature of the pipe through which the aqueous solution flows can be suppressed to an appropriate range, which is preferable from the viewpoint of heat resistance of the pipe and energy consumption. The concentration of the aqueous solution is more preferably 60 to 82% by weight, still more preferably 65 to 80% by weight.
In addition, since the salt which consists of 1,6-hexamethylenediamine and adipic acid which is a raw material of polyamide 66 is not so high in solubility in water, it is known that the salt recrystallizes and precipitates at a high concentration. Yes. Therefore, it is necessary to adjust the concentration of the salt in the aqueous solution to about 50% by weight. Furthermore, even if it is 50% by weight or less, recrystallization is likely to occur when the temperature of the aqueous solution is low. Therefore, measures such as positively heating and keeping the piping line are necessary. For this reason, it is technically difficult to increase the concentration of the aqueous salt solution in the raw material adjustment step. On the other hand, the salt of 1,5-pentamethylenediamine and adipic acid, which is a raw material of polyamide 56, is a salt with extremely high solubility in water, and therefore, 1,6-hexamethylenediamine, which is a raw material of polyamide 66 resin, A 50% by weight aqueous solution of an equimolar salt with adipic acid starts recrystallization when the liquid temperature drops below 40 ° C., whereas 50% by weight of an equimolar salt of 1,5-pentamethylenediamine and adipic acid. It was found that the% aqueous solution was not recrystallized even at a liquid temperature of 5 ° C. and kept in a uniform dissolved state. For this reason, it has been found that a high concentration raw material aqueous solution can be prepared in advance, and the concentration can be increased with almost no volatilization of 1,5-pentamethylenediamine.

  Next, when the aqueous solution temperature in the raw material adjusting step is in the range of 10 to 50 ° C., the solubility of the salt of 1,5-pentamethylenediamine and adipic acid in water increases, and the energy required for keeping the piping line warm. This is preferable because consumption is suppressed. More preferably, it is 20-40 degreeC.

The preferred heat polymerization method of the present invention undergoes a step of concentrating the aqueous solution after the raw material adjustment step (concentration step). In the concentration step, the concentration of the aqueous solution is concentrated to 80 to 95% by weight, and then subjected to the pressurization step. Is essential. The concentration of the aqueous solution is preferably 80% by weight or more because the volatilization amount of 1,5-pentamethylenediamine in the polymerization step can be suppressed. On the other hand, it is preferable that the concentration of the aqueous solution is 95% by weight or less because a prepolymer is easily generated in the pressure control step. Therefore, the concentration of the aqueous solution at the end of the concentration step is more preferably 83 to 93% by weight, and still more preferably 85 to 90% by weight. At this time, it is preferable to keep the temperature of the aqueous solution at 150 ° C. or lower, and by concentrating in this temperature range, water can be actively evaporated while suppressing volatilization of 1,5-pentamethylenediamine. More preferably, it is 140 degrees C or less, More preferably, it is 130 degrees C or less, Most preferably, it is 100-120 degreeC. For the same reason, it is preferable to adjust the valve of the polymerization can so as to maintain the pressure (gauge pressure) in the polymerization can at 0.05 to 0.5 MPa, and it is possible to keep it at 0.1 to 0.4 MPa. More preferred. The concentration time may be appropriately selected so that the concentration of the aqueous solution falls within the above range, but is preferably approximately 0.5 to hours.

  In the preferred heat polymerization method described above, since the concentration of the aqueous solution of the salt charged in the polymerization can is high, the absolute amount of volatilized water is small, and the aqueous solution is concentrated at a relatively low temperature and slightly pressurized in the concentration step. The amount of 1,5-pentamethylenediamine that volatilizes in the polymerization step can be greatly reduced. This makes it possible to control the amino end group concentration and the concentration ratio of the amino end group to the carboxyl end group in the obtained polyamide 56 resin. In the heat polymerization method that satisfies the above requirements, the molar ratio of 1,5-pentamethylenediamine and adipic acid present in the aqueous solution in the raw material adjustment step is preferably adjusted in the range of 0.95 to 1.05, Furthermore, the amino terminal group concentration in the polymer can also be controlled by adjusting the temperature, pressure, and treatment time in the can in the pressure control step, pressure release step, and pressure reduction step. Moreover, the method of using another amine compound and carboxylic acid compound as a terminal blocker as needed, and the method of adjusting a terminal group as a copolymerization component are also employable as needed. And by adding an antioxidant or heat stabilizer at any stage until the heat polymerization is completed, the polymerization reaction in the polymerization can easily proceeds, and the concentration balance of amino terminal groups and carboxyl terminal groups is balanced. A polyamide 56 resin having excellent heat resistance is obtained.

For the steps other than the above in the polymerization step, known methods described in, for example, JP-A No. 2003-292612 and JP-A No. 2004-075932 can be adopted. Explained.
In the pressurization step, the inside of the polymerization system is preferably a closed system, the aqueous solution is heated to generate water vapor, and the pressure is preferably increased to a desired pressure in the subsequent pressure control step. The time required for the pressure increase is preferably in the range of 0.1 to 2 hours. Thereby, the temperature in the polymerization can can be increased uniformly, and the cyclization reaction of 1,5-pentamethylenediamine can be suppressed, which is preferable.

  In the pressure control step, it is preferable to generate the prepolymer while heating the inside of the polymerization system and maintaining the pressurized state. The internal pressure (gauge pressure) at this time is preferably 1 to 2 MPa because volatilization of 1,5-pentamethylenediamine is suppressed and a prepolymer is easily formed. The internal pressure of the can may be adjusted by a technique such as adjusting the opening / closing degree of a valve connected to the outside world. Moreover, it is preferable to set it as 180-280 degreeC, and, as for the temperature in a can, it is more preferable to set it as 200-270 degreeC.

  In the pressure releasing step, the inside of the polymerization can is preferably returned to normal pressure, and the temperature in the can is preferably made higher than the melting point of the prepolymer. It is preferable to adjust the time required for releasing the pressure within a range of 0.1 to 3 hours so that 1,5-pentamethylenedidiamine remaining unreacted hardly volatilizes. More preferably, it is 0.2-2 hours, More preferably, it is 0.3-1 hour. And it is preferable to raise the temperature in a superposition | polymerization can over the melting | fusing point of a prepolymer over the said time, specifically, it is preferable to set it as 220-270 degreeC. More preferably, it is 230-260 degreeC.

  In the decompression step, polycondensation proceeds by heating the temperature in the polymerization can above the melting point of the produced polymer. On the other hand, since the thermal decomposition of the polymer can be suppressed by suppressing to an appropriate temperature, the temperature in the polymerization can is preferably 240 to 300 ° C.

  Moreover, since the water generated by polycondensation can be removed out of the system by lowering the pressure in the polymerization can and the reaction can easily proceed, the pressure in the polymerization can (gauge pressure) is -5 to -50 kPa. It is preferable to adjust within the range.

  In the discharging step, an inert gas such as nitrogen may be injected into the polymerization can and the pressure (gauge pressure) in the polymerization can may be increased to 0.1 to 2 MPa to discharge the polymer. By cooling the discharged polymer with water and cutting it, a pellet-like polyamide 56 resin can be obtained.

  The obtained polyamide 56 resin can be subjected to solid phase polymerization as required, but it is preferable in terms of cost and quality to obtain a desired degree of polymerization only by a heat polymerization method. In the case of solid-phase polymerization, the pelletized polyamide 56 resin is treated in a temperature range of 130 to 220 ° C. for 1 to 48 hours under vacuum or in a nitrogen atmosphere to obtain resin pellets having a target degree of polymerization. be able to.

Next, the spinning and crimping method of the present invention will be described.
Using the polyamide 56 resin produced by the heat polymerization method as described above, a highly oriented undrawn yarn is obtained by a specific spinning method, and then crimped to obtain the crimped yarn of the present invention. As described above, due to its molecular structure, the polyamide 56 resin is hardly gelled by melt spinning even if it contains many amino end groups, and exhibits good spinnability. The reason why the polyamide 56 has higher heat resistance to melting than the polyamide 66, that is, it is difficult to gel when melted, is considered to be because the carbon number of the methylene chain to which the amino terminal group is bonded is short. In other words, in the polyamide 66, the amino terminal group is bonded to the methylene chain having 6 carbon atoms, so that the molecular chain near the amino terminal end is easily returned, and the reductant is liberated by thermal decomposition and induces gelation. On the other hand, it is presumed that polyamide 56 has a methylene chain having 5 carbon atoms and is therefore difficult to be converted due to steric hindrance.
Since the polyamide 56 resin contains a lot of water in an undried state, it is easily hydrolyzed and cannot be used for melt spinning as it is. Therefore, it is necessary to heat and dry under some heat medium or vacuum to lower the moisture content to about 100 to 1500 ppm. Since the polyamide 56 tends to have a yolk when dried under air, it is preferably dried under nitrogen or vacuum or a combination thereof. What is necessary is just to change a drying temperature suitably so that it may become the said moisture content. The moisture content after drying is preferably 200 to 1300 ppm, and more preferably 300 to 1100 ppm. Here, the moisture content is a value measured at 180 ° C. using a Karl Fischer coulometric titration moisture meter.

  Next, the dried pellet is fiberized in a spinning process. As the polyamide 56 to be used for fiberization, the polyamide 56 having a relative viscosity of sulfuric acid of 2.0 to 3.5 and an Mw / Mn of 1.5 to 3.0 produced by the method described above is used. The polyamide 56 is fiberized by, for example, a spinning device (schematic diagram) shown in FIG. First, the polyamide 56 pellets charged into the hopper 1 are melted by the extruder 2 and transferred to the gear pump block 3 built in the extruded spinning block 4. Further, the yarn is sent to a spinning pack 5 incorporated in the spinning block 4 and the polymer is filtered in the pack, and then discharged from the spinneret 6 to obtain a yarn 8. The spun yarn 8 is once cooled and solidified by the cooling chimney 7, then given an oil agent by the oil supply device 9, appropriately entangled by the entanglement nozzle 10, and then taken up by the godet rolls 11 and 12. The fiber package 14 is obtained by being wound by the winder 13. In addition, in order to remove the low melting point substance sublimated from the fiber, a suction device may be provided directly under the base. The spinning temperature at the time of melt spinning is preferably 20 to 60 ° C. higher than the melting point of the polyamide 56 in order to stabilize the discharge at the die and to improve the spinnability, and at a temperature 25 to 55 ° C. higher. More preferably. Also, in order to suppress the precipitation of monomers and oligomers during spinning and to improve the spinnability, a 2-20 cm heating cylinder, polymer oxidation deterioration, or air for preventing contamination of the nozzle holes, steam, nitrogen, etc. Inert gas generators such as may be installed.

  The spinning oil may be attached straight to the yarn, but in order to adhere more uniformly, it is dispersed in water at 1 to 50% by weight, preferably 5 to 30% by weight, and attached to the fiber as a water emulsion oil. It is important that the yarn temperature at this time is lower than the glass transition point of the polyamide 56. By attaching the spinning oil within this range, the scuff resistance with the oiling device can be suppressed, so that the spinnability is dramatically improved. The preferred yarn temperature at the position where the spinning oil is adhered is 5 to 40 ° C. Further, the spinning oil may be attached in two or three stages. For example, after a relatively low concentration water emulsion oil agent having a concentration of 1 to 20% by weight is attached in order to converge the yarn once at a position of 0.5 to 2 m directly below the base, the entanglement treatment is performed before winding. It is also preferable to deposit a relatively medium or high concentration water emulsion oil agent at a concentration of 10 to 50% by weight at an arbitrary position. For spinning oils, false twist heater contamination during post-crimping (false twisting), slip prevention with twisted body (yarn threadability, improved twist number on false twist heater), multi It is important to improve fiber migration within the filament. For this purpose, it is preferable to use an oil containing a smoothing agent having good heat resistance, a high coefficient of friction between the fibers and the twisted body, and a low coefficient of friction between the fibers and the fibers. For example, a compound obtained by copolymerizing an alkylene oxide having 2 to 4 carbon atoms with an alcohol having one or more hydroxyl groups in the molecule and a compound derived therefrom are preferably used.

  As the alcohol, any natural or synthetic monohydric alcohol having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, butanol, isoamyl alcohol, 2-ethylhexanol, lauryl alcohol, isotridecyl alcohol, isocetyl alcohol, stearyl alcohol) , Isostearyl alcohol, etc.), dihydric alcohols (ethylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, etc.) and trihydric or higher alcohols (glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, etc.). .

  The alkylene oxide having 2 to 4 carbon atoms includes ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide (hereinafter abbreviated as BO), tetrahydrofuran (hereinafter referred to as THF). Abbreviations). When EO is copolymerized with other alkylene oxide, the ratio of EO needs to be 50 to 80% by weight. If the EO ratio is less than 50% by weight, the viscosity becomes too high, and if it exceeds 80% by weight, the heat resistance becomes poor. The addition mode may be either random addition or block addition. The average molecular weight of the smoothing agent is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 10,000 in terms of smoothness and heat resistance. The content of these smoothing agents is adjusted to 55% by weight or more based on the whole oil agent, and as other components, ionic surfactants, nonionic surfactants, bundling agents, rust preventives, antiseptics, antioxidants A paste property improver, an antistatic agent, a pH lowering inhibitor, and a water resistance agent may be added as appropriate. Further, it is preferable that the spinning oil is adhered to 0.2 to 2.0% by weight as a pure oil (excluding water) with respect to the whole fiber. The said characteristic is exhibited effectively by making the adhesion amount of an oil agent into 0.2 weight%. On the other hand, when the adhesion amount of the oil exceeds 2.0% by weight, the false twisting heater, the roll, and the twisted body become very dirty. More preferably, it is 0.3-1.5 weight%, More preferably, it is 0.4-1.0 weight%.

  The entanglement nozzle 10 may be installed on the spinning line as shown in FIG. 1, or may be installed between the godet rolls or before the winder. When it is desired to increase the degree of entanglement (CF value), it is preferably installed between godet rolls having a low yarn tension or before the winder, and when it is desired to reduce the CF value, it is preferably installed on the spinning line.

  The take-up speeds of the godet rolls 11 and 12 are set so that the elongation of the multifilament is 25 to 99% in order to improve the crimping processability, which is a subsequent process, and the mechanical properties and dyeing quality of the fiber. For this purpose, the speed of the godet roll 11 (corresponding to the spinning speed) is preferably 3000 to 7000 m / min. More preferably, it is 3500-6000 m / min, More preferably, it is 4000-5500 m / min.

  In addition, the polyamide 56 fiber of the present invention has extremely high hygroscopicity, and oriented crystallization occurs due to moisture absorption in the spinning process. That is, even after the thinning is completed on the spinning line, crystallization occurs sequentially and the dimensions change. Therefore, in order to stabilize the fiber structure, the godet roll 11 is stretched by 0.1 to 20% between the godet roll 11 and the godet roll 12, that is, the speed of the godet roll 12 is set 0.1 to 20% faster than the speed of the godet roll 11. It is preferable to increase the molecular orientation. The stretch rate is more preferably 0.5 to 15%, and still more preferably 2 to 10%.

  Further, the polyamide 56 fiber of the present invention is likely to cause saddles (ear standing) because the internal strain of the fiber is relaxed (contracted) after being wound around the package. This is considered to be derived from the molecular structure of polyamide 56. Although the crystal structure of the polyamide 56 fiber has not yet been clarified, as described above, moisture is absorbed on the spinning line and after packaging, and orientational crystallization occurs. For this reason, after spinning, the saddle is easily relaxed and contracted to form a saddle.

  In order to eliminate the saddle, it is necessary to remove the internal strain of the fiber between melt spinning and winding, and it is effective to wind in a relaxed state. In the relaxed state, that is, the winding speed is slower than that of the godet roll 12, and the winding is performed. The winding tension at that time (the tension between the final godet roll 12 and the winding machine 13) is preferably 0.05 cN / dtex or more in order to prevent reverse winding on the godet roll 12, and the distortion of the fiber internal structure Is preferably 0.3 cN / dtex or less. A more preferable winding tension is 0.07 to 0.25 cN / dtex, and further preferably 0.09 to 0.2 cN / dtex.

  As described above, stretching is applied between the godet rolls, and the fiber package 14 having a stable structure with a small amount of delayed shrinkage can be obtained by releasing the distortion of the internal structure of the fiber while relaxing at the time of winding and winding with low tension.

  Moreover, it is preferable to make the load with respect to the line length which a roller bail or a drive roll is contacting the package (equivalent to the pressure with respect to a package. Hereinafter, it is called a surface pressure) into the range of 6-20 kg / m. By setting the surface pressure to 6 kg / m or more, an appropriate hardness can be given to the fiber package, and the collapse of the fiber package and saddle can be suppressed. Moreover, the collapse of a fiber package and a bulge can be suppressed by making surface pressure into 20 kg / m or less. A more preferable range is 8 to 16 kg / m. In addition, by setting the twill angle in the range of 5 to 10 °, it is possible to obtain a stable unwinding tension even at a high speed unwinding while suppressing yarn dropping on the fiber package end surface, and to prevent yarn breakage to the end surface portion. it can. More preferably, it is 5.5 to 8 °, and further preferably 5.8 to 7 °. It is also important to change the twill angle to suppress the ribbon. As a means for this, it is preferable that the twill angle is swung within a certain range (within a center value of ± 1.5 °) or the winding ratio (ratio of spindle rotation speed and traverse cycle) is constant. Further, a method of rapidly changing the twill angle in the ribbon generation zone region is also preferably used, and these methods may be combined. Further, since the polyamide 56 has a very low bending rigidity and a strong behavior as an elastic body, it is necessary to devise a method for sufficiently following the yarns when turning back during traverse. For this reason, a 1- to 3-axis blade traverse method with high-speed followability, a microcam traverse with good thread gripping properties, and a spindle traverse capable of shortening the free length are preferably used. Taking advantage of each characteristic, it is more preferable to use a micro cam traverse method at a winding speed of 3000 to 4000 m / min, and a 1-axis to 3-axis blade traverse system when the winding speed exceeds 4000 m / min.

  The drive system at the time of winding is generally driven by a drive roller, but a spindle driving system and a method of forcibly driving a roller bail of the winder are preferably used. When the roller bail is forcibly driven, the roll bail speed relative to the package surface speed is always controlled to be 0.05 to 1% overfeeding, and the package foam can be further improved.

  Next, the crimping process will be described with reference to FIG. 2 (schematic diagram). First, the yarn 15 is pulled out from the cheese 14 and supplied to the supply roller 19 through the yarn path guides 16 to 18. Thereafter, the yarn 15 is heat treated by the first heater 20 while being twisted by the twisted body 23, and the structure is fixed by the cooling plate 22 through the yarn path guide 21. At this time, the tension measured between the cooling plate 22 and the twisted body 23 was taken as the twisting tension (T1), and the tension measured between the twisted body 23 and the stretching roller 24 was taken as the untwisting tension (T2). . The structure-fixed yarn 15 is supplied to the second heater 25 via the drawing roller 24, and then wound as a crimped yarn package 29 via the yarn path guides 27 and 28 via the delivery roller 26. In the present invention, the process between the drawing roller 24 and the delivery roller 26 is very important for obtaining a polyamide 56 crimped yarn having excellent flexibility. Moreover, you may arrange | position various guides, tension control apparatuses, fluid processing apparatuses, oil supply apparatuses, etc. as needed in the apparatus of FIG.

  In the case of the yarn contact type, the temperature of the first heater 20 is preferably in the range of 150 to 230 ° C. When the temperature of the first heater is 150 ° C. or higher, the crimp of the obtained crimped yarn can be fixed, and an excellent crimp property (CR) and shrink property (SW) can be obtained. Further, since the melting point of the polyamide 56 is around 260 ° C. at the maximum, the upper limit temperature is 230 ° C. from the viewpoint of process passability. Therefore, the temperature of the first heater 20 is more preferably 160 to 220 ° C, and even more preferably 170 to 210 ° C, from the viewpoint of good process passability, mechanical properties, and crimped quality. Moreover, when the 1st heater 20 is a non-contact type, since the thread breakage by abrasion resistance can be suppressed and productivity improves, it is more preferable. When a non-contact heater is used, the heater temperature may be appropriately changed so that the yarn temperature at the non-contact heater outlet is 150 to 230 ° C.

  Moreover, it is preferable that the speed ratio of the supply roller 19 and the extending | stretching roller 24 in false twisting, ie, a process magnification, is 1.0-1.7 times. If the processing magnification is 1.0 times or more, the twisting tension (T1) in the false twisting process is increased, and a high twist number is given to the yarn in the first heater 20, so that the crimping property (CR) is excellent. It becomes a crimped yarn. Further, by setting the processing magnification to 1.7 times or less, it is possible to perform a stable false twisting process, and it is possible to obtain a crimped yarn excellent in quality with less fluff. The processing magnification is more preferably 1.05 to 1.6 times, and still more preferably 1.1 to 1.5 times.

  Further, in the crimped yarn of the present invention, the second heater 25 is provided as described above in order to give high flexibility, stretch properties and moisture absorption / release properties, and relaxation heat treatment is performed between the drawing roller 24 and the delivery roller 26. It is preferable. The polyamide 56 fiber has a lower elastic modulus than the general-purpose polyamide 6 and polyamide 66 and is excellent in flexibility. However, the flexibility and moisture absorption can be increased by controlling the structure of the amorphous part. The control of the amorphous part in false twisting can be controlled to some extent by the processing magnification, the first heater temperature, and the processing tension, but effectively depends on the heat treatment temperature and relaxation rate in the second heater 25. Is. The temperature of the second heater 25 is preferably 120 to 200 ° C. By setting the heater temperature to 120 ° C. or higher, the molecular mobility of the oriented amorphous part can be increased and the molecular orientation can be effectively reconstructed. Moreover, by setting the heater temperature to 200 ° C. or lower, excessive molecular mobility can be suppressed, and molecular alignment spots in the fiber longitudinal direction can be suppressed. Further, the temperature of the second heater 25 is preferably lower than the temperature of the first heater 20. The temperature of the 2nd heater 25 becomes like this. More preferably, it is 140-190 degreeC, More preferably, it is 150-180 degreeC. Moreover, it is more preferable that it is 10 degreeC or more lower than the temperature of the 1st heater 20, and it is still more preferable that it is 20 degreeC or more lower. In addition, when the 2nd heater 25 is a non-contact heater, the yarn temperature of the heater exit vicinity should just be 120-200 degreeC. Further, if the relaxation rate between the drawing roller 24 and the delivery roller 26 is in the range of 5 to 25%, it is possible to obtain a good crimped yarn while maintaining the running stability of the yarn. 8 to 20% is more preferable. More preferably, it is 10 to 18%.

  The ratio of the peripheral speed (D) of the twisted body 23 and the speed (Y) of the stretching roller 24 (hereinafter referred to as D / Y) is preferably in the range of 1.1 to 2.4. By setting D / Y to 1.1 or more, the balance between twisting tension and untwisting tension is good, and false twisting without fuzz and yarn breakage can be performed. Moreover, the surface wear of the twisted body 23 is suppressed by setting D / Y to 2.4 or less, and there is no crimp in the yarn longitudinal direction even in continuous operation over a long period of time. False twisting without yarn breakage is possible. D / Y is more preferably 1.15 to 2.2, and still more preferably 1.2 to 2.0.

  Moreover, a belt nip type friction false twisting tool can be preferably used as the twisted body 22. The angle formed by doubling the angle between the belt rotation axis that is horizontal in the belt rotation direction and the yarn travel axis that is horizontal in the direction in which the yarn travels is not particularly limited. A range of 90 to 120 ° is preferable because the yarn can be efficiently twisted and the wear of the belt itself can be kept low. Furthermore, although the surface material is not particularly limited, chloropyrene rubber or nitrile butylene rubber can be preferably used. At this time, nitrile butylene rubber is more preferable from the viewpoint of durability, cost, and flexibility. Further, if the surface hardness of the belt nip type friction false twister is 60 to 80 degrees, it is possible to suppress the cross-sectional deformation of the polyamide 56, suppress the shaving of the yarn, and improve the wear of the belt body. A range of 65 to 75 degrees is more preferable.

  In addition, by winding the crimped yarn so that the winding tension becomes 0.02 to 0.10 cN / dtex, the delayed recovery rate of the wound yarn is lowered, and the difference between the inner and outer layers of the fiber properties due to the tightening is reduced. it can. Furthermore, it is possible to obtain a crimped yarn package having a good winding shape while suppressing saddles and bulges.

  The crimped yarn obtained by the above-described method is used for process passage in a higher order process, for example, when used for weaving and knitting, in order to suppress as much as possible the rubbing between fibers and yarn path guides, knitting needles, etc. Preferably it is done. As the oil to be applied, it is preferable to use an oil containing a smoothing agent having a high effect of reducing the coefficient of friction between the fibers and the metal. For example, fatty acid ester, polyhydric alcohol ester, ether ester, silicone, mineral oil and the like are preferable. These smoothing agents may be used as a single component, but a plurality of components may be mixed and used in consideration of convergence, antistatic properties, and heat resistance. As more preferred smoothing agents, fatty acid esters and mineral oils can be selected. The fatty acid ester is not particularly limited, and examples thereof include monohydric alcohols and monohydric carboxylic acids such as methyl oleate, isopropyl myristate, octyl palmitate, oleyl laurate, oleyl oleate, and isotridecyl stearate. Monohydric alcohols such as esters, dioctyl sebacate, dioleyl adipate, and esters of polyvalent carboxylic acids, polyhydric alcohols such as ethylene glycoldiolate, trimethylolpropane tricaprylate, glycerol trioleate, and monovalents Examples thereof include esters of carboxylic acids and alkylene oxide addition esters such as lauryl (EO) n octanoate. The content of these smoothing agents is adjusted to 50 to 95% by weight based on the whole oil agent, and other components include ionic surfactants, nonionic surfactants, bundling agents, rust inhibitors, preservatives, and antioxidants. An agent, a penetrating agent, a surface tension reducing agent, a phase inversion viscosity reducing agent, an adhesive property improving agent, an antistatic agent, a pH lowering inhibitor, and a water resistance agent may be added as appropriate.

  The crimped yarn thus obtained can be used as a fiber structure. For example, the crimped yarn can be suitably used for clothing as a final product after making the knitted fabric into a woven or knitted fabric by a conventional method.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the measuring method in an Example used the following method.

A. Sulfuric acid relative viscosity (ηr)
0.25 g of a sample (resin, fiber) was dissolved to 100 g of sulfuric acid having a concentration of 98% by weight, and the flow time (T1) at 25 ° C. was measured using an Ostwald viscometer. Subsequently, the flow-down time (T2) of only 98% by weight sulfuric acid was measured. The ratio of T1 to T2, that is, T1 / T2, was defined as sulfuric acid relative viscosity.

B. Mw / Mn
A sample (resin, fiber) was washed with hot water at 90 ° C. for 30 minutes and then vacuum-dried at 90 ° C. to a moisture content of 1000 ppm, and dissolved in hexafluoroisopropanol to obtain a measurement solution. This was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of PMMA, and Mw / Mn was determined. The measurement conditions are as follows.
GPC device: Waters 510
-Column: Two Shodex GPC HFIP-806Ms connected together and used-Solvent: Hexafluoroisopropanol-Temperature: 30 ° C
・ Flow rate: 0.5 ml / min ・ Sample concentration: 2 mg / 4 ml
Filtration: 0.45 μm-DISMIC 13HP (Toyo filter paper)
・ Injection volume: 100 μl
Detector: differential refractometer RI (Waters 410)
Standard: PMMA (concentration: sample 0.25 mg / solvent 1 ml)
Measurement time: 62 minutes
C. 1 g of amino end group concentration sample (resin, fiber) was dissolved in 50 mL of a phenol / ethanol mixed solution (phenol / ethanol = 80/20) by shaking at 30 ° C., and this solution was dissolved in 0.02N hydrochloric acid. Neutralization titration was performed to determine the amount of 0.02N hydrochloric acid required. Only the phenol / ethanol mixed solvent (the same amount as above) was neutralized and titrated with 0.02N hydrochloric acid to determine the amount of 0.02N hydrochloric acid required. And the amino terminal group amount per 1 ton of sample was calculated | required from the difference.

D. Carboxyl end group concentration sample (resin, fiber) 0.5 g was dissolved in 196 ± 1 ° C. benzyl alcohol 20 ml, this solution was neutralized and titrated with 0.02 N potassium hydroxide / ethanol solution and required 0.02 N. The amount of potassium hydroxide / ethanol solution was determined. Further, only 20 ml of the benzyl alcohol was neutralized and titrated with a 0.02N potassium hydroxide / ethanol solution, and the amount of the required 0.02N potassium hydroxide / ethanol solution was determined. And the amount of carboxyl end groups per 1 ton of the sample was calculated | required from the difference.

E. Melting point and heat of fusion In a differential calorific curve obtained by measuring 10 mg of a sample (resin, fiber) at a heating rate of 16 ° C./min using a DSC-7 differential scanning calorimeter manufactured by PerkinElmer, on the endothermic side The peak showing the extreme value was judged as the melting peak, and the temperature giving the extreme value was defined as the melting point (° C.). When a plurality of extreme values exist, the extreme value on the high temperature side was taken as the melting point. Moreover, the heat capacity calculated | required from the area of a melting peak was integrated | accumulated (when it has a some melting peak, it combined), and it was set as the calorie | heat amount of fusion.

F. Using a fineness measuring instrument, a skein having a total length of 100 m was made while applying a tension of 0.18 cN / dtex, and the total fineness was determined by measuring the weight and multiplying by 100. The single fiber fineness was determined by dividing the fineness by the number of constituent filaments.

G. Strength, elongation, 5% elongation stress Measured according to JIS L1013 chemical fiber filament yarn test method (1995). Note that a load-elongation curve was obtained with a gripping interval of 200 mm and a tensile speed of 200 mm / min. Next, the strength and elongation were obtained by dividing the load value indicating the maximum point by the fineness to obtain the strength, and dividing the elongation at the maximum point load by the initial sample length to obtain the elongation. The measurement environment was a temperature of 20 ° C. and a relative humidity of 65%. The 5% elongation stress was determined by dividing the strength at 5% elongation by the fineness. The measurement was performed 5 times and the average value was taken.

H. After storing the fiber package for 24 hours or more in an atmosphere having a boiling water shrinkage rate of 20 ° C. and a relative humidity of 65%, a cassette is prepared using the measuring machine in the atmosphere to measure the original length L0. Subsequently, it was treated with boiling water for 15 minutes under no load, and the cassette was air-dried for one day and night, and then L1 was measured and determined by the following formula.
Boiling water shrinkage rate (%) = [(L0−L1) / L0)] × 100 (%)
L0: Raw length measured with sample taken and measured under initial load of 0.09 cN / dtex L1: Case measured with L0 measured in boiling water for 15 minutes, air-dried for 1 day and night, initial load 0 Case length under 0.09 cN / dtex
I. Expansion / contraction recovery rate (CR value)
After storing the fiber package in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% for at least 24 hours, the crimped yarn is removed using a measuring machine in the atmosphere, and the load is substantially free of load. Treated in boiling water for 15 minutes and air dried for 24 hours. The sample was immersed in water under a load equivalent to 0.088 cN / dtex, and the skein length L′ 0 after 2 minutes was measured. Next, the skein length L′ 1 after 2 minutes was measured after exchanging with a fine load equivalent to 0.0018 cN / dtex except for the case corresponding to 0.088 cN / dtex in water. And the expansion-contraction restoration rate (CR value) was calculated by the following formula.

CR (%) = [(L′ 0−L′1) / L′ 0] × 100 (%)
J. et al. Hygroscopic parameter △ MR
About 1 g of a sample (crimped yarn) is knitted with a cylinder knitting machine, the weight when the knitted fabric is completely dried, and an atmosphere of 20 ° C., relative humidity 65% or 30 ° C., relative humidity 90%, constant temperature and humidity From the change in weight with the weight after treatment for 24 hours using a vessel (Espec PL-4SPH manufactured by Tabai), the following formula was used.
Moisture absorption rate (%) = [(weight after moisture absorption−weight when absolutely dry) / weight when absolutely dry] × 100
The moisture absorption rate at 20 ° C. and relative humidity 65% measured above is “MR1”, the moisture absorption rate at 30 ° C. and 90% relative humidity is “MR2”, and the moisture absorption / release parameter ΔMR (%) is MR2 to MR1. Asked to reduce. Here, the moisture absorption / desorption parameter ΔMR is a driving force for obtaining comfort by releasing moisture in the clothes to the outside air when the clothes are worn, and is 30 when performing light to medium work or light to medium exercise. It is the difference in moisture absorption between the temperature in clothes represented by 90 ° C. and a relative humidity of 90% and the outside air temperature represented by 20 ° C. and a relative humidity of 65%. The larger the hygroscopic parameter ΔMR used in the present invention, the higher the hygroscopic property, and the better the comfort when worn.

K. A 10% elongation recovery rate sample was stretched to 10% of the gripping interval at a gripping interval of 20 cm and a pulling speed of 10 cm / min using a TENSILON UCT-100 manufactured by Orientec Co., Ltd., and immediately deweighted and recorded. The elongation recovery rate was determined from the hysteresis curve.
Elongation recovery rate (%) = (β / α) × 100
α: Elongation at 10% elongation β: Recovery elongation to the point where the stress becomes equal to the initial load U%
The thickness unevenness U% (Normal) in the longitudinal direction of the yarn was measured with UT-4 manufactured by Zervegar Worcester. The measurement conditions were a yarn speed of 200 m / min and a measurement of 1 minute at a twister speed of 12000 rpm to obtain an average deviation rate (U%).

M.M. CF value JIS L1013 (chemical fiber filament yarn test method) was measured under the conditions indicated by the degree of entanglement in 7.13. The number of tests was 50, and the CF value (Coherence Factor) was determined from the average value L (mm) of the entanglement length according to the following formula.

CF value = 1000 / L
N. A light fastness tubular knitted fabric was prepared and refined at 80 ° C. for 30 minutes in sodium carbonate, 1% owf, sandet CL-80, 2% owf, bath ratio 1:40. The cylindrical knitting is dyed at 95 ° C. for 40 minutes with an acidic dye 0.5% owf, a bath ratio of 1:30, pH = 7, washed with water, and dried with hot air at 50 ° C. for about 6 hours to obtain a dyed fabric. It was. Subsequently, the light fastness test was conducted according to the dye fastness test method for ultraviolet carbon arc lamp light of JIS L0842 (2004). The 10-hour irradiation was grade 3, the 20-hour irradiation was grade 4 and the 40-hour irradiation was grade 5, and the fading of the sample was graded on a gray scale on the basis of blue scale fading.

O. After the dyed fabric prepared in the washing fastness term P was treated by the method described in JIS L0844 (A-2) (2004), the degree of fading before and after washing was graded according to the following criteria using a gray scale.
5th grade: No fading was observed.
4th grade: Almost no fading.
3rd grade: Slight fading is observed.
Second grade: Fading is observed.
Level 1: Fading is severe.

P. Friction fastness was measured for the dyed fabric prepared in Section P of Friction Fastness according to the measurement of the drying test of JIS L0849 (2004) 7.1. For the test, cut the dyed cloth and make a test side with a length of 23 cm and a width of 3 cm, and attach it to a friction fastness tester type II (Gakushin type, manufactured by Daiei Kagaku Seiki Co., Ltd., model RT-200). 3) is a friction element, the load of the friction element is 1.96 N, and reciprocating friction is performed 10 times per minute between 10 cm of test pieces. The degree of contamination of the white cotton cloth after 100 reciprocating frictions was determined using the gray scale for contamination specified in JIS L0805 (2005).

Q. Hand feeling (flexibility) and swell feeling when gripping the dyed fabrics created in Examples and Comparative Examples with the palm of the hand ◎ (excellent), ○ (good), △ (equivalent to conventional products), × (inferior) The four grades were evaluated.

[Adjustment Example 1] (Adjustment of lysine decarboxylase)
E. First. E. coli strain JM109 was cultured as follows. First, this platinum strain was inoculated into 5 ml of LB medium, and precultured by shaking at 30 ° C. for 24 hours. Next, 50 ml of LB medium was placed in a 500 ml Erlenmeyer flask and preliminarily steam sterilized at 115 ° C. for 10 minutes. The strain was precultured in this medium, and cultured for 24 hours under the condition of 30 cm in amplitude and 180 rpm while adjusting the pH to 6.0 with 1N aqueous hydrochloric acid. The bacterial cells thus obtained were collected and a cell-free extract was prepared by ultrasonic disruption and centrifugation. These lysine decarboxylase activities were measured by a standard method (reference: Kenji Sokota, Haruo Misono, Biochemistry Experiment Course, vol.11, P.179-191 (1976)).
When lysine is used as a substrate, conversion by lysine monooxygenase, lysine oxidase, and lysine mutase, which are considered to be the main main pathways, can occur. The cell-free extract of E. coli strain JM109 was heated. Furthermore, this cell-free extract was fractionated with 40% saturated and 55% saturated ammonium sulfate. Using this crude purified lysine decarboxylase solution, 1,5-pentamethylenediamine was produced from lysine.

[Adjustment Example 2] (Adjustment of 1,5-pentamethylenediamine)
An aqueous solution prepared to be 50 mM lysine hydrochloride (manufactured by Wako Pure Chemical Industries), 0.1 mM pyridoxal phosphate (manufactured by Wako Pure Chemical Industries), 40 mg / L-crudely purified lysine decarboxylase (prepared in Reference Example 1) The mixture was reacted at 48 ° C. for 36 hours while maintaining the pH at 5.5 to 6.5 with 0.1N hydrochloric acid aqueous solution to obtain 1,5-pentamethylenediamine hydrochloride. By adding sodium hydroxide to this aqueous solution, 1,5-pentamethylenediamine hydrochloride is converted to 1,5-pentamethylenediamine, extracted with chloroform, and distilled under reduced pressure (1.33 kPa, 60 ° C.). As a result, 1,5-pentamethylenediamine was obtained.

[Preparation Example 3] (Preparation of 60% by weight aqueous solution of 1,5-pentamethylenediamine adipate)
When an aqueous solution obtained by dissolving 510 g of 1,5-pentamethylenediamine produced in Production Example 2 in 827 g of water is immersed in a water bath at 41 ° C. and stirred, about 5 g of adipic acid (manufactured by Kirk) is added. About 1 g was added in the vicinity of the neutralization point, and the change in pH of the aqueous solution relative to the amount of adipic acid added was examined. The neutralization point was determined to be pH 8.32. The amount of adipic acid added at the neutralization point was 730 g. A 60% by weight aqueous solution (2067 g) of an equimolar salt of 1,5-pentamethylenediamine and adipic acid was adjusted so that the pH was 8.32.

Example 1
1,5-pentamethylenediamine and water were added to 60% by weight aqueous solution of the equimolar salt of 1,5-pentamethylenediamine and adipic acid obtained in Preparation Example 3, and 1,5-pentamethylene present in the aqueous solution was added. The ratio of the number of moles of diamine to the number of moles of adipic acid was adjusted to 1.004, and the concentration of the raw material in the aqueous solution was adjusted to 60% by weight, and the mixture was charged in a heating medium heating polymerization can previously purged with nitrogen. Next, the jacket was heated while the inside of the can was purged with nitrogen to concentrate the aqueous solution. At this time, it was concentrated until the concentration of the raw material in the aqueous solution became 89% by weight while controlling the temperature in the can to 120 ° C. and the pressure in the can (gauge pressure) to 0.2 MPa. The concentration of the aqueous solution in the can was judged from the amount of distilled water. Subsequently, the polymerization kettle was sealed and raised to 270 ° C., and the pressure was increased until the internal pressure of the can reached 1.7 MPa. Further, the internal pressure of the can was controlled at 1.7 MPa, and the internal temperature of the can was adjusted to 250 ° C. Thereafter, the temperature was raised to 285 ° C., and the pressure was gradually released to atmospheric pressure over 60 minutes. The internal pressure of the can was reduced to -12 kPa, and the polymerization reaction was stopped when the predetermined stirring power was reached. Finally, the inside of the polymerization can was slightly pressurized with nitrogen to discharge the polymer, and the discharge gut was cooled with water and then cut to obtain a polyamide 56 resin chip. The polyamide 56 resin had sulfuric acid relative viscosity ηr: 2.76, Mw / Mn: 1.74, amino end group concentration: 52 eq / ton, [NH ₂ ] / [COOH]: 1.08, melting point: 254 ° C. It was.

  The obtained polyamide 56 resin was dried for 2 hours in a can with a rotary drier at a temperature of 80 ° C. in a nitrogen atmosphere, then heated to 100 ° C. and vacuum dried for 5 hours. The moisture content of the obtained polyamide 56 was about 300 ppm. Next, using the spinning device shown in FIG. 1, a spinning temperature of 280 ° C., a cooling air speed of 25 m / min (cooling air temperature: 21 ° C.), a spinning oil adhesion amount of 0.6% by weight (10% water emulsion) 6 wt% adhesion), entanglement pressure 0.3 MPa, first godet roll peripheral speed 4400 m / min, second godet roll peripheral speed 4500 m / min, winding tension 0.18 cN / dtex, 96 dtex, 60 filament high An oriented undrawn yarn package was obtained. The spinneret used has a hole diameter of 0.20 mm, a hole depth of 0.80 mm (L / D: 4), an entire surface arrangement of 60 holes, and the filter layer filter is a 10 μm cut nonwoven fabric filter.

  The undrawn yarn package has a fiber winding amount of 6 kg, no saddle and bulge, strength: 4.15 cN / dtex, elongation: 59%, U% (Normal) 0.3%, CF value 5.5. It was. Further, the unstretched yarn was subjected to a false twisting apparatus shown in FIG. 24), DY ratio 1.60, relaxation rate 10% (between stretching roller 24 and delivery roller 26), false twisting at a processing speed of 500 m / min (peripheral speed of stretching roller 24), 84 dtex A 60-filament crimped yarn was obtained.

As shown in Table 1, the obtained crimped yarn has sulfuric acid relative viscosity ηr: 2.78, Mw / Mn: 1.76, amino end group concentration: 51 eq / ton, [NH ₂ ] / [COOH]: 1. 04, melting point: 254 ° C., heat of fusion 78 J / g, 5% elongation stress 0.45 cN / dtex, boiling water shrinkage 3.8%, stretching / restoring rate (CR) 33%, moisture absorption / desorption parameter ΔMR 4.1% The 10% elongation recovery rate was 85%. The fabric made of the crimped yarn was much superior in flexibility, stretchability, and moisture absorption / release properties than the fabric made of the conventional polyamide fiber. In addition, the dyeability (coloring property) was equivalent to that of conventional polyamide fibers, and the light fastness and friction fastness were also excellent.

Comparative Example 1
An aqueous solution in which the ratio of the number of moles of 1,6-hexamethylenediamine to the number of moles of adipic acid is 1.004 and the concentration of the raw material in the aqueous solution is 50% by weight is charged into a polymerization can and the jacket temperature is 280 ° C. Heating was started. When the pressure in the polymerization can (gauge pressure) is adjusted to 1.47 MPa, the temperature in the can is raised to 270 ° C., then the pressure in the can is gradually released, and after further reducing pressure, a predetermined stirring power is reached. The polymerization reaction was stopped. Subsequently, the discharged strand was cooled with water and cut to obtain polyamide 66 resin.

The obtained polyamide 66 resin was dried in the same manner as in Example 1 to obtain a polyamide having a moisture content of 300 ppm. The polyamide 66 resin had a sulfuric acid relative viscosity ηr: 2.72, Mw / Mn: 1.83, amino end group concentration: 54 eq / ton, [NH ₂ ] / [COOH]: 1.10, melting point: 265 ° C. It was. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. Comparative Example 1 was slightly lightly dyed as compared to Example 1, and was further inferior in flexibility and moisture absorption / release.

Comparative Example 2
A 120 liter stainless steel autoclave was charged with 40 kg of ε-caprolactam aqueous solution (containing 15% water), the inside of the can was purged with nitrogen, sealed, and heated until the inside temperature of the can reached 255 ° C. At this time, the internal pressure of the can was adjusted so that the internal pressure (gauge pressure) did not exceed 1.5 MPa, and the polymerization reaction was allowed to proceed while stirring. After the internal temperature of the can reached 250 ° C., the internal pressure of the can was gradually released to atmospheric pressure, and when the predetermined stirring power was reached, the polymerization reaction was stopped. The inside of the polymerization can was slightly pressurized with nitrogen to discharge the polymer into a strand, which was cut after water cooling to obtain a polyamide 6 resin. Further, the obtained polyamide 6 resin was boiled with hot water at 98 ° C. and treated for 10 hours to remove residual monomers.

The obtained polyamide 6 resin was dried in the same manner as in Example 1 to obtain a polyamide having a moisture content of 300 ppm. The polyamide 6 resin had a sulfuric acid relative viscosity ηr: 2.70, Mw / Mn: 1.82, amino end group concentration: 52 eq / ton, [NH ₂ ] / [COOH]: 1.06, melting point: 225 ° C. It was. Using this polyamide resin, a 84 dtex, 60 filament crimped yarn was obtained in the same manner as in Example 1 except that the first heater temperature during false twisting was 190 ° C. The evaluation results are shown in Table 1. Although the comparative example 1 showed the color development property equivalent to Example 1, it was inferior to a softness | flexibility and moisture absorption / release property.

Example 2
A polyamide 56 resin was obtained in the same manner as in Example 1 except that the polymerization reaction was stopped by adjusting the reaching value of the stirring power in the polymerization process of the polyamide 56 resin. The sulfuric acid relative viscosity of Example 2 was 2.15, Mw / Mn: 1.78, amino end group concentration: 47 eq / ton, [NH ₂ ] / [COOH]: 1.07, and melting point: 253 ° C. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. Example 2 was inferior in elasticity and strength to Example 1, but the other characteristics were good.

Example 3
A polyamide 56 resin was obtained in the same manner as in Example 1 except that the polymerization reaction was stopped by adjusting the reaching value of the stirring power in the polymerization process of the polyamide 56 resin. The sulfuric acid relative viscosity of Example 3 was 3.25, Mw / Mn: 2.25, amino end group concentration: 44 eq / ton, [NH ₂ ] / [COOH]: 1.17, and melting point: 254 ° C. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. In Example 3, yarn breakage during spinning was slightly high. Moreover, although the softness | flexibility and the elasticity were inferior to Example 1, the characteristic superior to the conventional polyamide type crimped yarn was shown.

Comparative Example 3
A polyamide 56 resin was obtained in the same manner as in Example 1 except that the polymerization reaction was stopped by adjusting the reaching value of the stirring power in the polymerization process of the polyamide 56 resin. The relative viscosity of sulfuric acid in Comparative Example 3 was 1.95, Mw / Mn: 1.77, amino end group concentration: 48 eq / ton, [NH ₂ ] / [COOH]: 1.07, and melting point: 253 ° C. When spinning was performed using the polyamide resin, the strength of the obtained undrawn yarn was 2.35 cN / dex, which was considerably lower than that of Example 1. Although the undrawn yarn was false twisted to obtain a crimped yarn, it had low strength and low crimpability, and was inferior to conventional polyamide-type crimped yarn.

Comparative Example 4
After heating the polyamide 56 resin of Example 1 at a heating rate of 30 ° C./hour so that the internal temperature of the can becomes 140 ° C. with a rotary dryer, the heating rate is then adjusted so that the internal temperature of the can becomes 170 ° C. The temperature was raised at 10 ° C./hour. Moreover, pressure reduction was started after the can internal temperature reached 100 ° C., and the pressure was reduced to a can internal pressure of 0.1 kPa. After reaching 170 ° C., solid-state polymerization was performed for about 3 hours, and then gradually flowing nitrogen to return to normal pressure. After cooling the chip to a can internal temperature of 80 ° C., the chip was extracted. Sulfuric acid relative viscosity ηr: 3.6, Mw / Mn: 2.45, amino end group concentration: 38 eq / ton, [NH ₂ ] / [COOH]: 0.93, melting point: 254 ° C. Met. As a result of spinning in the same manner as in Example 1 using the polyamide resin, there were more yarn breaks than in Example 3. Further, the flexibility and stretchability were inferior to those of Example 3.

Example 4
The ratio of the number of moles of 1,5-pentamethylenediamine present in the aqueous solution to the number of moles of adipic acid was adjusted to 1.002, and the concentration of the raw material in the aqueous solution was adjusted to 60% by weight. In the process, after raising the internal temperature of the can to 265 ° C., the internal pressure of the can was gradually released and the polymerization reaction was stopped when the predetermined stirring power was reached. Obtained.
The obtained polyamide 56 resin was dried in the same manner as in Example 1 to obtain a polyamide having a moisture content of 300 ppm. The polyamide 56 resin had a sulfuric acid relative viscosity ηr: 2.76, Mw / Mn: 1.55, amino end group concentration: 51 eq / ton, [NH ₂ ] / [COOH]: 1.04, melting point: 254 ° C. It was. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. Example 4 showed the characteristic excellent in the softness | flexibility and moisture absorption / release property similarly to Example 1. FIG.
Example 5
In the process of polymerizing the polyamide 56 resin, the temperature in the can was raised to 280 ° C., then the pressure in the can was gradually released, and the polymerization reaction was stopped when the predetermined stirring power was reached. Thus, a polyamide 56 resin was obtained.
The obtained polyamide 56 resin was dried in the same manner as in Example 1 to obtain a polyamide having a moisture content of 300 ppm. The polyamide 56 resin had a sulfuric acid relative viscosity ηr: 2.75, Mw / Mn: 2.32, amino end group concentration: 52 eq / ton, [NH ₂ ] / [COOH]: 1.15, melting point: 254 ° C. It was. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. In Example 5, yarn breakage during spinning and false twisting was greater than in Example 1. Although the strength was slightly low, there was no practical problem. Further, the fabric characteristics such as flexibility and moisture absorption / release were almost the same as those in Example 1.

Comparative Example 5
In the process of polymerizing the polyamide 56 resin, the temperature in the can was raised to 290 ° C., then the pressure in the can was gradually released, and the polymerization reaction was stopped when the predetermined stirring power was reached. Thus, a polyamide 56 resin was obtained.
The obtained polyamide 56 resin was dried in the same manner as in Example 1 to obtain a polyamide having a moisture content of 300 ppm. The polyamide 66 resin had a sulfuric acid relative viscosity ηr: 2.78, Mw / Mn: 3.05, amino end group concentration: 48 eq / ton, [NH ₂ ] / [COOH]: 0.72, melting point: 254 ° C. It was. Using the polyamide resin, a crimped yarn of 84 dtex and 60 filaments was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. In Comparative Example 5, yarn breakage at the time of spinning sporadically occurred and the spinnability was very poor, and the undrawn yarn obtained had a very uneven U% (Normal) of 3.3%. Moreover, the processing tension in false twisting was not stable, and the fabric made of the obtained crimped yarn had a feeling of coarseness and poor quality.

Example 6
A crimped yarn was obtained in the same manner as in Example 1 except that the relaxation rate during false twisting was 5% (between the drawing roller 24 and the delivery roller 26). The obtained crimped yarns are as shown in Table 1. 5% elongation stress is 1.0 cN / dtex, boiling water shrinkage rate is 7.6%, stretch recovery rate (CR) is 48%, moisture absorption and desorption parameter ΔMR3 0.7%, 10% elongation recovery rate was 88%. The fabric made of the crimped yarn was slightly inferior to that of Example 1, but exhibited a texture superior to that of a fabric made of a conventional polyamide fiber. Further, light fastness and friction fastness were excellent as in Example 1.

Comparative Example 6
A crimped yarn in the same manner as in Example 1 except that the relaxation rate during false twisting was 0% (between the drawing roller 24 and the delivery roller 26) and the second heater temperature was not heated (about 20 ° C.). Got. The obtained crimped yarns are as shown in Table 1 and have 5% elongation stress of 1.4 cN / dtex and an expansion / contraction recovery ratio of 56%, both of which are higher than those of Example 1 and have a feeling of coarseness and fukuroki. It was a texture.

Example 7
A crimped yarn was obtained in the same manner as in Example 1 except that the relaxation rate during false twisting was 15% (between the drawing roller 24 and the delivery roller 26) and the second heater temperature was 160 ° C. The crimped yarn of Example 7 has a 5% elongation stress of 0.25 cN / dtex, a melting point: 254 ° C., a heat of fusion of 75 J / g, a boiling water shrinkage of 2.2%, a stretching / restoring ratio (CR) of 25%, and an absorption / release. Wet parameter ΔMR 4.4%, 10% elongation recovery rate 80%. The fabric made of the crimped yarn was more flexible than Example 1 and had a cool feeling of contact due to its excellent moisture absorption and desorption properties, and exhibited optimum characteristics for inner use.

Example 8
A crimped yarn was obtained in the same manner as in Example 7, except that the relaxation rate during false twisting was 18% (between the drawing roller 24 and the delivery roller 26). Although the crimped yarn of Example 8 was excellent in flexibility, the 10% elongation recovery rate was 75% and the stretch back property tended to decrease.

Example 9
1,5-pentamethylenediamine and adipic acid are added to a 60% by weight aqueous solution of an equimolar salt of 1,5-pentamethylenediamine, and 1,5-pentamethylenediamine and water are added to form a mole, Polymerization, spinning, and false twisting were performed in the same manner as in Example 1 except that the ratio with the number of moles of adipic acid was adjusted to 0.994. The polyamide 56 resin had sulfuric acid relative viscosity ηr: 2.75, Mw / Mn: 1.88, amino end group concentration: 27 eq / ton, [NH ₂ ] / [COOH]: 0.30, melting point: 254 ° C. It was. The level of Example 9 was slightly lighter than that of Example 1. Further, the moisture absorption / release parameter ΔMR was slightly low at 3.5 and the dyeing fastness was slightly inferior, but the texture such as flexibility was excellent.

Example 10
1,5-pentamethylenediamine and adipic acid are added to a 60% by weight aqueous solution of an equimolar salt of 1,5-pentamethylenediamine, and 1,5-pentamethylenediamine and water are added to form a mole, Polymerization, spinning, and false twisting were carried out in the same manner as in Example 1 except that the ratio with the number of moles of adipic acid was adjusted to 1.008. The polyamide 56 resin had sulfuric acid relative viscosity ηr: 2.76, Mw / Mn: 1.78, amino end group concentration: 78 eq / ton, [NH ₂ ] / [COOH]: 2.6, melting point: 254 ° C. It was. The level of Example 10 was slightly darker than that of Example 1 and excellent in color development, and other characteristics were also excellent as in Example 1.

1: Hopper 2: Extruder 3: Gear pump block 4: Spinning block 5: Spinning pack 6: Spinneret 7: Cooling chimney 8: Yarn 9: Lubricating device 10: Entangling nozzle 11: First godet roll 12: Second godet roll 13 : Winding machine 14: Fiber package (cheese package)
15: Yarn 16-18: Yarn path guide 19: Supply roller 20: First heater 21: Yarn path guide 22: Cooling plate 23: Twist body 24: Stretching roller 25: Second heater 26: Delivery roller 27, 28: Yarn Path Guide 29: Crimped Yarn Package

Claims (8)

A crimped yarn comprising a polyamide 56 having a relative viscosity of sulfuric acid of 2.0 to 3.5 and Mw / Mn of 1.5 to 3, and having the following characteristics.
5% elongation stress: 0.2 to 1.0 cN / dtex
Boiling water shrinkage: 1-15%
Expansion and contraction rate: 10 to 55%
Hygroscopic parameter △ MR: 3% or more The crimped yarn according to claim 1, wherein a 10% elongation recovery rate is 80% or more. The crimped yarn according to claim 1 or 2, wherein the amino terminal group concentration is 25 to 80 eq / ton. The crimped yarn according to any one of claims 1 to 3, wherein the amino terminal group concentration and the carboxyl terminal group concentration satisfy the following relationship.
0.5 ≦ [NH 2] / [COOH] ≦ 2.0
[NH2]: Amino end group concentration of crimped yarn (eq / ton)
[COOH]: Carboxyl end group concentration of crimped yarn (eq / ton)   The crimped yarn according to any one of claims 1 to 4, wherein the crimped yarn is a false twisted yarn. A crimped yarn, wherein the polyamide 56 according to any one of claims 1 to 5 is synthesized using a bio-derived compound. The bio-derived compound according to claim 6 is glucose and / or lysine, and the compound is synthesized from 1,5 pentamethylenediamine synthesized by one or more reactions selected from an enzyme reaction, a yeast reaction and a fermentation reaction. A crimped yarn characterized by using polymerized polyamide 56 as a diamine component. A fiber structure comprising the crimped yarn according to any one of claims 1 to 7 .

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