JP5098693B2 - Liquid crystal polyester fiber - Google Patents

Description

  The present invention relates to a liquid crystal polyester fiber having high strength and high elastic modulus, excellent heat resistance and thermal dimensional stability, small single fiber fineness, and excellent uniformity and wear resistance in the longitudinal direction of the fiber.

  Liquid crystalline polyester is a polymer composed of rigid molecular chains. In melt spinning, the molecular chains are highly oriented in the fiber axis direction, and further subjected to heat treatment (solid phase polymerization). It is known that the highest strength and elastic modulus can be obtained. In addition, it is also known that liquid crystal polyester has an increased molecular weight due to solid-phase polymerization and an increased melting point, thereby improving heat resistance and dimensional stability (see Non-Patent Document 1). Thus, liquid crystal polyester fibers exhibit high strength, high elastic modulus, excellent heat resistance, and thermal dimensional stability by solid phase polymerization.

  On the other hand, the liquid crystalline polyester fiber has a rigid molecular chain highly oriented in the fiber axis direction and a dense crystal is formed. Therefore, the interaction in the direction perpendicular to the fiber axis is low, and fibrils are easily generated by friction, resulting in wear resistance. Has the disadvantage of being inferior.

  Solid-phase polymerization of liquid crystal polyester fibers is industrially adopted as a method of processing fibers by packaging them from the viewpoint of simplifying equipment and improving productivity, but solid-state polymerization proceeds. There is a problem in that fusion between single yarns is likely to occur in a temperature range that can be obtained, and the fused portion is peeled off during unwinding from the package shape. Defects deteriorate the uniformity in the longitudinal direction of the fiber, such as a decrease in strength, and also cause problems such as fiber fibrillation starting from the defects.

  In recent years, especially for filters made of monofilaments and scissors for screen printing, there has been a growing demand for higher density of woven fabric (higher mesh), reduction of wrinkle thickness, and larger area of opening (opening) to improve performance. In order to achieve this, there is a strong demand for fineness and high strength of the single fiber fineness, and at the same time, there is a demand for reducing defects in the opening for high performance. The defects of the opening are caused by the above-described fibrils caused by friction in the fiber manufacturing process or the high-order processing process, and therefore, the strength in the fiber longitudinal direction, the improvement in the uniformity of the fineness, and the improvement in the abrasion resistance of the fiber are required.

  In addition, deterioration in process passability in high-level fiber processing such as weaving is caused by fibril catching or tension fluctuation due to fibril deposition on the guide, improving the fiber longitudinal strength, fineness uniformity, and fiber abrasion resistance. There is a need for improvement in performance.

  For improving the abrasion resistance of the liquid crystal polyester fiber, the core component is a liquid crystal polyester and the sheath component is a core / sheath type composite fiber (see Patent Document 1), the island component is a liquid crystal polyester, and the sea component is a flexible thermoplastic. A sea-island type composite fiber made of a polymer has been proposed (see Patent Document 2). Although these technologies can achieve improved wear resistance by forming a fiber surface with a flexible polymer, the fiber strength is inferior due to the high fraction of components other than liquid crystal polyester, which is necessary for increasing the strength of liquid crystal polyester. In the solid phase polymerization of such fibers, there is a problem that the surface of the fiber having a low melting point is easily fused and defects are easily generated. Furthermore, in the core-sheath composite spinning as in Patent Document 1, the discharge amount of each core-sheath is smaller than that of single component spinning, and when the discharge amount is further reduced for fineness, the residence time is increased. As a result, the melt viscosity is changed due to gelation or degradation decomposition, resulting in a problem that thick unevenness and composite abnormality occur in the longitudinal direction of the fiber and the uniformity in the longitudinal direction is impaired. Further, in blend spinning as in Patent Document 2, if the discharge amount is reduced for fineness, the effect of blend unevenness in the longitudinal direction becomes obvious and the uniformity in the longitudinal direction is impaired.

  These problems are caused by the combination of liquid crystal polyester and other components, which makes it possible to simultaneously achieve finer, higher strength, high longitudinal uniformity and wear resistance with a single component of liquid crystal polyester. A technology that can do this has been desired.

  By the way, regarding the fiberization of the modified liquid crystal polyester, a technology that can increase the strength without using solid phase polymerization by using a liquid crystal polyester having a specific composition and performing melt spinning with a nozzle having a tapered introduction portion has been proposed. (See Patent Document 3). However, the fineness obtained by this technique is 19 dtex at the minimum, and fineness reduction cannot be achieved. Moreover, although this technique is high in strength, there is a problem that thermal dimensional stability and elastic modulus are inferior because solid phase polymerization is not performed. Furthermore, the taper nozzle used in this technique is inferior in spinning stability due to unstable streamlines, and a small amount of sample is obtained, but long-time spinning is difficult, and spinning that is particularly important for fineness When the speed is increased, there is a problem that the yarn forming property is further deteriorated.

Further, in solid phase polymerization in a package state, the specific surface area increases as the fineness of the single fiber becomes finer, so that the contact points between the single fibers increase and fusion occurs easily in the solid phase polymerization. Therefore, the fineness in the longitudinal direction of the fiber and the uniformity of the strength are further deteriorated as the fineness is reduced. Patent Document 3 discloses an example in which solid-phase polymerization is performed, but the single fiber fineness is as thick as 51 dtex. Regarding the technique for improving the fusion in the solid-phase polymerization when the liquid crystal polyester having a characteristic composition is made finer, Nothing is suggested.
Edited by Technical Information Association, “Modification of liquid crystal polymer and latest applied technology” (2006) (pages 235-256) JP-A-1-229815 (first page) JP 2003-239137 A (first page) JP 2006-89903 A (first page)

  The object of the present invention is to achieve a high woven density and a reduced thickness without impairing the characteristics of solid-state polymerized liquid crystal polyester fibers such as high strength, high elastic modulus, excellent heat resistance, and thermal dimensional stability. Another object of the present invention is to provide a liquid crystal polyester fiber having improved single-fiber fineness, high strength, excellent uniformity in the longitudinal direction of the fiber, and excellent wear resistance.

  The present inventors have found that the above-described problems can be solved by using a liquid crystal polyester having a specific composition and further improving the spinning conditions such as melt spinning and solid phase polymerization.

That is, the present invention is represented by the following structural units (I), (II), (III), a liquid crystal polyester consisting of (IV) and (V), meets the following conditions 1 to 4, structural units (I) is structure 40 to 85 mol% based on the sum of units (I), (II) and (III), and structural unit (II) is 60 to 90 mol% based on the sum of structural units (II) and (III) The structural unit (IV) is a liquid crystal polyester fiber characterized by being 40 to 95 mol% with respect to the total of the structural units (IV) and (V) .
that's all

Condition 1. In differential calorimetry, the heat of fusion (ΔHm1) at the endothermic peak (Tm1) observed when measured under the temperature rising condition from 50 ° C. to 20 ° C./min is held at a temperature of Tm1 + 20 ° C. for 5 minutes after the observation of Tm1. Then, the temperature is once cooled to 50 ° C. under a temperature lowering condition of 20 ° C./min, and 3 times the heat of fusion (ΔHm2) in the endothermic peak (Tm2) observed when measured again under the temperature rising condition of 20 ° C./min. More than 0 times.
Condition 2. The peak half-width at Tm1 is less than 15 ° C.
Condition 3. Single fiber fineness is 18.0 dtex or less.
Condition 4. The strength is 14.0 cN / dtex or more and the elastic modulus is 600 cN / dtex or more.

  Weaving density is increased and thickness is reduced without impairing the characteristics of the woven fabric made of solid-state polymerized liquid crystal polyester fibers such as high strength, high elastic modulus, excellent heat resistance and thermal dimensional stability. And fabric quality can be improved, especially for filters and screen printing ridges. To improve performance, weaving density is increased (high mesh), ridge thickness is reduced, and opening (opening) is large. , Reduction of defects in the opening, and improvement of weaving can be achieved.

  Hereinafter, the liquid crystal polyester fiber of the present invention will be described in detail.

  The liquid crystalline polyester used in the present invention is a polyester capable of forming an anisotropic molten phase upon melting, and comprises the following structural units (I), (II), (III), (IV) and (V). In the present invention, the structural unit refers to a unit that can constitute a repeating structure in the main chain of the polymer.

  An important technique in the present invention is a combination of these five components. This combination results in the molecular chain having the proper crystallinity and non-linearity, ie, a melt-spinnable melting point. Therefore, the fiber has good spinning performance at the spinning temperature set between the melting point of the polymer and the thermal decomposition temperature, and a uniform fiber can be obtained in the longitudinal direction. Can be increased. Furthermore, in the present invention, it is important to combine components composed of diols that are not bulky and have high linearity like the structural units (II) and (III). By combining these components, the molecular chains in the fiber have an ordered and less disturbed structure, and the crystallinity is not excessively increased and the interaction in the direction perpendicular to the fiber axis can be maintained. Thereby, in addition to high strength and elastic modulus, excellent wear resistance is also obtained.

  In the present invention, the above structural unit (I) is preferably 40 to 85 mol%, more preferably 65 to 80 mol%, still more preferably based on the total of the structural units (I), (II) and (III). 68 to 75 mol%. By setting it as such a range, crystallinity can be made into an appropriate range, high intensity | strength and an elasticity modulus are obtained, and melting | fusing point also becomes the range which can be melt-spun.

  The structural unit (II) is preferably 60 to 90 mol%, more preferably 60 to 80 mol%, still more preferably 65 to 75 mol%, based on the total of the structural units (II) and (III). By setting it as such a range, since crystallinity does not become high too much and the interaction of a fiber axis perpendicular | vertical direction can be maintained, abrasion resistance can be improved.

  The structural unit (IV) is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%, based on the total of the structural units (IV) and (V). By setting such a range, the melting point of the polymer becomes an appropriate range, and has a good spinning property at a spinning temperature set between the melting point of the polymer and the thermal decomposition temperature. Uniform fibers can be obtained.

Particularly preferred ranges of the respective structural units of the liquid crystal polyester used in the present invention are as follows. The liquid crystal polyester fiber of the present invention can be suitably obtained by adjusting the composition so as to satisfy the above conditions within this range.
Structural unit (I) 45-65 mol%
Structural unit (II) 12-18 mol%
Structural unit (III) 3 to 10 mol%
Structural unit (IV) 5-20 mol%
Structural unit (V) 2-15 mol%
In addition to the above structural units, the liquid crystalline polyester used in the present invention includes aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids such as 1, cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, chlorohydroquinone, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone An aromatic diol such as p-aminophenol and the like may be copolymerized within a range of about 5 mol% or less without impairing the effects of the present invention.

  Further, in the range of about 5% by weight or less which does not impair the effects of the present invention, a vinyl polymer such as polyester, polyolefin or polystyrene, polycarbonate, polyamide, polyimide, polyphenylene sulfide, polyphenylene oxide, polysulfone, aromatic polyketone, aliphatic polyketone, Polymers such as semi-aromatic polyester amide, polyether ether ketone and fluororesin may be added. Polyphenylene sulfide, polyether ether ketone, nylon 6, nylon 66, nylon 46, nylon 6T, nylon 9T, polyethylene terephthalate, polypropylene Suitable are terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethanol terephthalate, polyester 99M, etc. And the like as. When these polymers are added, the melting point thereof is preferably within the melting point ± 30 ° C. of the liquid crystalline polyester so as not to impair the spinning property.

  Furthermore, within the range not impairing the effects of the present invention, various metal oxides, kaolin, silica and other inorganic substances, colorants, matting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents In addition, various additives such as a fluorescent brightening agent, a terminal group blocking agent, and a compatibilizing agent may be contained in a small amount.

  The polystyrene-equivalent weight average molecular weight (hereinafter referred to as molecular weight) of the liquid crystalline polyester fiber of the present invention is preferably from 25 million to 1550,000. Having a high molecular weight of 255,000 or more has high strength, elongation, and elastic modulus and improves textile performance. In particular, when the fineness is reduced, the shock absorption is increased and the yarn breaks in higher processes. And the wear resistance is improved. Moreover, since it has a high melting point, it has excellent heat resistance. Since these characteristics improve as the molecular weight increases, it is preferably 30 million or more, more preferably 350,000 or more. The upper limit of the molecular weight is not particularly limited, but the upper limit that can be reached in the present invention is about 1550,000. The molecular weight referred to in the present invention is a value determined by the method described in the examples.

  In the fiber of the present invention, the heat of fusion (ΔHm1) at the endothermic peak (Tm1) observed when the temperature is measured at 50 ° C. to 20 ° C./min in differential calorimetry is Tm1 + 20 ° C. after the observation of Tm1. After being held at temperature for 5 minutes, it is once cooled to 50 ° C. under a temperature drop condition of 20 ° C./min, and the heat of fusion (ΔHm 2) at the endothermic peak (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./min. ) Is 3.0 times or more, preferably 4.0 times or more, more preferably 6.0 times or more.

  In this measurement method, ΔHm1 represents the degree of crystallization of the fiber (crystallinity), and ΔHm2 represents the degree to which the liquid crystal polyester constituting the fiber is crystallized in the process of re-heating after being once melted and cooled and solidified. When ΔHm1 is 3.0 times or more than ΔHm2, the degree of crystallinity of the fiber is sufficiently high, and high strength and elastic modulus can be obtained. However, if the crystallinity is excessively high, the toughness of the fiber is impaired and the workability is deteriorated. Therefore, ΔHm1 is preferably 15.0 times or less than ΔHm2. In the liquid crystalline polyester fiber of the present invention, there is one endothermic peak at the time of temperature increase and re-temperature increase under the above-described measurement conditions, but two or more peaks are observed depending on the structural change due to the solid phase polymerization conditions and the like. May be. In this case, ΔHm1 is a value obtained by summing the heat of fusion of all endothermic peaks in the temperature raising process, and ΔHm2 is a value obtained by summing the heat of fusion of all endothermic peaks in the reheating temperature process.

  An important technique for achieving the present invention is to control ΔHm1 within the above-mentioned range. The liquid crystalline polyester of the present invention has a low ΔHm1 and cannot be said to have sufficiently high strength and elastic modulus only by spinning under normal spinning conditions. Therefore, it is important to increase ΔHm1, and in order to achieve this efficiently, it is preferable to solid-phase polymerize the fiber, and in order to increase productivity, it is more preferable to solid-phase polymerize the fiber in a packaged state. By applying solid phase polymerization, ΔHm1 is greatly increased, and the strength and elastic modulus are increased. The absolute value of ΔHm1 varies depending on the composition of the structural unit of the liquid crystal polyester, but is preferably 5.0 J / g or more, more preferably 6.0 J / g or more, and even more preferably 7.0 J / g or more. The larger ΔHm1, the higher the degree of crystallinity, the greater the strength and elastic modulus of the fiber, and the better the heat resistance. Therefore, the mechanical properties and heat resistance of products such as textiles can be improved, especially when the fineness is reduced. The process passability can be improved. The upper limit of ΔHm1 is not particularly limited, but the upper limit that can be achieved in the present invention is about 20 J / g.

  Further, the fiber of the present invention has a peak half width at Tm1 of less than 15 ° C, preferably less than 13 ° C. The peak half width in this measurement method represents the completeness of the crystal, and it can be said that the smaller the full width at half maximum, the higher the completeness of the crystal. High crystal integrity increases fiber strength and elastic modulus, improves heat resistance, and improves mechanical properties and heat resistance when made into textiles and other products, especially through finer process steps Can be improved. The lower limit of the peak half-value width is not particularly limited, but the lower limit that can be achieved in the present invention is about 3 ° C.

  The melting point (Tm1) of the fiber of the present invention is preferably 300 ° C. or higher, more preferably 310 ° C. or higher, and further preferably 320 ° C. or higher. By having such a high melting point, heat resistance and thermal dimensional stability are excellent. In order to achieve a high melting point of the fiber, there are methods such as spinning a liquid crystal polyester polymer having a high melting point, in order to obtain a fiber having particularly high strength and elastic modulus and excellent longitudinal uniformity. For this, it is preferable to solid-phase polymerize melt-spun fibers.

  Tm2 strongly reflects the melting point of the liquid crystal polyester polymer constituting the fiber. Therefore, the higher the Tm2, the higher the heat resistance of the polymer. In the fiber of the present invention, Tm2 is preferably 290 ° C or higher, more preferably 310 ° C or higher. The upper limits of Tm1 and Tm2 are not particularly limited, but the upper limit that can be reached in the present invention is about 400 ° C.

  The single fiber fineness of the fiber of the present invention is 18.0 dtex or less. By reducing the single fiber fineness to 18.0 dtex or less, the flexibility of the fiber is improved, the processability of the fiber is improved, and the surface area is increased, so that the adhesiveness with a chemical such as an adhesive is increased. In addition to having a monofilament made of monofilaments, there are advantages that the thickness can be reduced, the woven density can be increased, and the opening (area of the opening) can be widened. The single fiber fineness is preferably 10.0 dtex or less, more preferably 7.0 dtex or less. The lower limit of the single fiber fineness is not particularly limited, but the lower limit that can be achieved in the present invention is about 1.0 dtex.

  The fineness variation rate of the fiber of the present invention is preferably 30% or less, more preferably 20% or less, and still more preferably 10% or less. The fineness fluctuation rate referred to in the present invention refers to a value measured by the method described in the examples. When the fineness variation rate is 30% or less, the uniformity in the longitudinal direction is increased, and the variation in fiber strength (product of strength and fineness) is also reduced. Since the variation is small, the uniformity of the opening (area of the opening) when the cocoon is made increases and the cocoon performance can be improved.

  The strength of the fiber of the present invention is 14.0 cN / dtex or more, preferably 18.0 cN / dtex or more, and more preferably 20.0 cN / dtex or more. The elastic modulus is 600 cN / dtex or more, more preferably 700 cN / dtex or more, and still more preferably 800 cN / dtex or more. The upper limits of the strength and elastic modulus are not particularly limited, but the upper limits that can be achieved in the present invention are a strength of about 30 cN / dtex and an elastic modulus of about 1500 cN / dtex. The strength referred to in the present invention refers to the tensile strength described in JIS L1013: 1999, and the elastic modulus refers to the initial tensile resistance. Since high strength and elastic modulus can exhibit high strength even at fineness, the fiber material can be made lighter and thinner, and yarn breakage in higher processing steps such as weaving can be suppressed. In the fiber of the present invention, high strength and elastic modulus can be obtained when ΔHm1 is 3.0 times or more than ΔHm2.

  Further, the strength fluctuation rate of the fiber of the present invention is preferably 20% or less, and more preferably 15% or less. The strength referred to in the present invention refers to the strength at the time of cutting in the measurement of tensile strength described in JIS L1013: 1999, and the strength fluctuation rate refers to a value measured by the method described in the examples. When the strength variation rate is 20% or less, the uniformity in the longitudinal direction is increased, and the variation in fiber strength (the product of strength and fineness) is also reduced. It is also possible to suppress yarn breakage in the high-order processing step.

  The elongation of the fiber of the present invention is preferably 2.0% or more. When the elongation is 2.0% or more, the impact absorbability of the fiber is increased, and the process passability and the handleability in the high-order processing step are excellent. The upper limit of elongation is not particularly limited, but the upper limit that can be reached in the present invention is about 10%.

  The fiber of the present invention has a compressive modulus (hereinafter referred to as a compressive modulus) in the direction perpendicular to the fiber axis is preferably 1.00 GPa or less, more preferably 0.50 GPa or less, and further preferably 0.35 GPa or less. The low compressive elastic modulus provides an effect of spreading the load by spreading the contact area when the fiber is pressed against the guide or ridge by a high-order processing step or a loom. Due to this effect, the pressing stress on the fiber is lowered and the wear resistance is improved. The lower limit of the compression elastic modulus is not particularly limited, but if it is 0.10 GPa or more, the fiber is not crushed and deformed, and the quality of the product is not impaired. In addition, the compression elastic modulus said by this invention points out the value calculated | required by the method of an Example description.

  The fiber of the present invention preferably has a thermal expansion coefficient of -20 to 0 ppm / ° C, more preferably -10 to 0 ppm / ° C. The thermal expansion coefficient referred to in the present invention refers to a value measured by the method described in the examples. Since the fiber of the present invention has a negative coefficient of thermal expansion and takes a low value of -20 to 0 ppm / ° C., the thermal dimensional stability is high, and high positional accuracy such as a circuit board base fabric and a circuit printing screen wrinkle is obtained. It can be suitably used for required applications.

  The birefringence (Δn) of the fiber of the present invention is preferably from 0.250 to 0.450, more preferably from 0.300 to 0.400. If Δn is within this range, the molecular orientation in the fiber axis direction is sufficiently high, and high strength and elastic modulus can be obtained.

  In the fiber of the present invention, the peak half-value width (Δ2θ) observed at 2θ = 18 to 22 ° in the equator direction with respect to the fiber axis in wide-angle X-ray diffraction is preferably less than 1.8 °. More preferably, it is less than When Δ2θ is as small as less than 1.8 °, the completeness of the crystal is high, and the strength and elastic modulus are high, so that the process passability is enhanced. The lower limit of Δ2θ is not particularly limited, but the lower limit is about 0.8 °. In the present invention, Δ2θ refers to a value obtained by the method described in the examples.

  The fiber of the present invention is preferably attached with an oil component for the purpose of improving the surface smoothness and the process passability by improving the wear resistance, and the oil adhesion amount is preferably 0.1% by weight or more based on the fiber weight. . In addition, the oil adhesion amount said by this invention refers to the value calculated | required by the method of an Example description. Since the effect increases as the amount of oil increases, it is more preferably 0.5% by weight or more, and further preferably 1.0% by weight or more. However, if there is too much oil, the adhesive strength between fibers increases and fibrillation occurs during unraveling, causing problems such as accumulation of oil on the guide and deterioration of processability. % Or less is more preferable, and 4% by weight or less is more preferable.

  The attached oil agent type is not particularly limited as long as it is generally used for fibers, but for liquid crystal polyester fibers, both prevention of fusion in solid phase polymerization and improvement of surface smoothness are achieved. It is preferable to use at least a polysiloxane compound having an effect. Among them, a polysiloxane compound that is liquid at room temperature (so-called silicone oil) that can be easily applied to fibers, particularly polydimethyl which is suitable for water emulsification and has a low environmental impact. It is particularly preferable to include a siloxane compound. In the present invention, it is determined by the method described in the examples that the adhered oil contains a polysiloxane compound.

  The abrasion resistance of the fiber of the present invention is preferably 5 seconds or more, and more preferably 10 seconds or more. The abrasion resistance referred to in the present invention refers to a value measured by the method described in the examples. When the wear resistance is 5 seconds or more, the generation of fibrils due to rubbing in the high-order processing step of the liquid crystal polyester fiber can be suppressed, and the uniformity in the longitudinal direction and the process passability are improved. Moreover, in the cocoon made of monofilament, clogging of the opening due to the fibrils being woven into the cocoon can be suppressed.

  The fibers of the present invention can have a wide number of filaments. The upper limit of the number of filaments is not particularly limited, but the number of filaments is preferably 50 or less, and more preferably 20 or less, in order to make the fiber product thinner and lighter. The filaments of the present invention are particularly suitable for monofilaments. To improve the performance of monofilament filters and printing screens, it is particularly required to increase the weaving density and the opening area. For this purpose, the fineness and the strengthening to ensure weaving are particularly strong. It has been demanded. However, if it is only finer and stronger, it can be obtained by solid-phase polymerization of the finer liquid crystalline polyester fiber, but conventional liquid crystalline polyester is inferior in wear resistance, and the weight of the finer finer is increased. Defects are generated due to an increase in fusion of the film, so that the uniformity in the longitudinal direction and the process passability are poor. The fibers of the present invention have wear resistance that can withstand weaving due to the properties of the polymer, and can be improved in process passability by being excellent in longitudinal uniformity.

  Hereafter, the manufacture example of the liquid crystalline polyester fiber of this invention is demonstrated in detail.

  The production method of the liquid crystalline polyester used in the present invention can be produced according to a known production method. For example, the following production methods are preferable, and in this case, the structural units (I) to (V) described above satisfy the conditions. It is necessary to adjust the amount of each monomer used.

  (1) Deacetic acid from acetoxycarboxylic acid such as p-acetoxybenzoic acid and diacetylated compounds of aromatic dihydroxy compounds such as 4,4′-diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a condensation polymerization reaction.

  (2) Hydroxycarboxylic acid such as p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid are reacted with acetic anhydride to produce phenol. A method for producing a liquid crystalline polyester by deacetic acid polycondensation reaction after acylating a functional hydroxyl group.

  (3) Dephenolization from phenyl esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a polycondensation reaction.

  (4) A predetermined amount of diphenyl carbonate is reacted with a hydroxycarboxylic acid such as p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid to form a diphenyl ester, and then 4,4′-dihydroxybiphenyl. A method for producing a liquid crystalline polyester by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as hydroquinone.

  Among them, hydroxycarboxylic acids such as p-hydroxybenzoic acid, aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid are reacted with acetic anhydride to produce phenolic compounds. A method of producing a liquid crystalline polyester by deacetic acid polycondensation reaction after acylating a hydroxyl group is preferred. Furthermore, the total amount of aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and the total amount of aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid are substantially equimolar. The amount of acetic anhydride used is preferably 1.12 equivalents or less, more preferably 1.10 equivalents or less of the total of the phenolic hydroxyl groups of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone. Preferably, the lower limit is 1.0 equivalent or more.

  When the liquid crystalline polyester used in the present invention is produced by a deacetic acid polycondensation reaction, a melt polymerization method in which the polycondensation reaction is completed by reacting under reduced pressure at a temperature at which the liquid crystalline polyester melts is preferable. For example, a predetermined amount of a hydroxycarboxylic acid such as p-hydroxybenzoic acid and an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid, and an acetic anhydride stirring blade, Charged into a reaction vessel equipped with a distillation pipe and provided with a discharge port at the bottom, heated under stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, then raised to the melting temperature of the liquid crystalline resin, and reduced pressure A method of completing the reaction by polycondensation is mentioned. The conditions for the acetylation are usually 130 to 300 ° C., preferably 135 to 200 ° C., usually 1 to 6 hours, preferably 140 to 180 ° C. for 2 to 4 hours. The polycondensation temperature is the melting temperature of the liquid crystal polyester, for example, in the range of 250 to 350 ° C., and preferably the melting point of the liquid crystal polyester polymer + 10 ° C. or higher. The degree of pressure reduction during polycondensation is usually 13.3 to 2660 Pa, preferably 1330 Pa or less, more preferably 665 Pa or less. In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

  The obtained polymer can be pressurized in the reaction vessel to, for example, about 0.1 ± 0.05 MPa at a temperature at which it melts and discharged in a strand form from the discharge port provided at the lower portion of the reaction vessel. The melt polymerization method is an advantageous method for producing a uniform polymer, and an excellent polymer with less gas generation can be obtained, which is preferable.

  When producing the liquid crystalline polyester used in the present invention, the polycondensation reaction can be completed by a solid phase polymerization method. For example, the liquid crystal polyester polymer or oligomer is pulverized by a pulverizer, and the melting point (Tm) -5 ° C. to the melting point (Tm) −50 ° C. (for example, 200 to 300 ° C.) of the liquid crystal polyester under a nitrogen stream or reduced pressure. A method of heating for 1 to 50 hours, polycondensing to a desired degree of polymerization, and completing the reaction can be mentioned.

  However, in spinning, if the liquid crystalline resin produced by the solid phase polymerization method is used as it is, the highly crystallized portion generated by the solid phase polymerization remains unmelted, which causes an increase in spinning pack pressure and foreign matter in the yarn. Since there is a possibility, it is preferable that the highly crystallized portion is completely melted by kneading (repletizing) once with a twin screw extruder or the like.

  The polycondensation reaction of the liquid crystal polyester proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The melting point of the liquid crystalline polyester polymer used in the present invention is preferably 200 to 370 ° C., more preferably 250 to 350 ° C., and further preferably 290 to 340 ° C. in order to widen the temperature range capable of melt spinning. In addition, melting | fusing point of a liquid crystalline polyester polymer points out the value measured by the method of an Example description.

  The melt viscosity of the liquid crystalline polyester polymer used in the present invention is preferably 0.5 to 200 Pa · s, particularly preferably 1 to 100 Pa · s, and more preferably 10 to 50 Pa · s from the viewpoint of spinnability. The melt viscosity is a value measured with a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1,000 (1 / s).

  The polystyrene equivalent weight average molecular weight (hereinafter referred to as molecular weight) of the liquid crystalline polyester used in the present invention is preferably 30,000 or more, and more preferably 50,000 or more. By setting the molecular weight to 30,000 or more, the spinning property can be improved with an appropriate viscosity at the spinning temperature, and the higher the molecular weight, the higher the strength, elongation and elastic modulus of the resulting fiber. On the other hand, if the molecular weight is too high, the viscosity becomes high, the fluidity is deteriorated, and finally the fluid does not flow. Therefore, the molecular weight is preferably less than 255,000, more preferably less than 150,000.

  In melt spinning, a known method can be used for melt extrusion of liquid crystal polyester, but an extruder type extruder is preferably used in order to eliminate the ordered structure generated during polymerization. The extruded polymer is measured by a known measuring device such as a gear pump through a pipe, and after passing through a filter for removing foreign matter, is guided to a base. At this time, the temperature from the polymer pipe to the die (spinning temperature) is preferably not less than the melting point of the liquid crystal polyester and the thermal decomposition temperature, more preferably not less than the melting point of the liquid crystal polyester + 10 ° C. and not more than 400 ° C. More preferably, the melting point is 20 ° C. or higher and 370 ° C. or lower. It is also possible to independently adjust the temperature from the polymer pipe to the base. In this case, the discharge is stabilized by making the temperature of the part close to the base higher than the temperature on the upstream side.

  In order to obtain the liquid crystal polyester fiber of the present invention, it is important to optimize the spinning conditions in order to obtain a fiber having a fineness and a low fineness variation rate using the liquid crystal polyester polymer composed of the above-described structural units. The liquid crystalline polyester polymer composed of the above-mentioned structural units can be spun at a wide range of spinning temperatures because of the large temperature difference between the melting point and the thermal decomposition temperature, and has a high thermal stability at the spinning temperature. Since fluidity is high and the thinning behavior of the polymer after ejection is stable, there is little fluctuation in fineness, which is advantageous for obtaining fibers with fineness and low fineness fluctuation rate. However, in order to uniformly obtain fibers with a single fiber fineness of 18 dtex or less, it is necessary to further increase the stability during discharge and the stability of the thinning behavior. In industrial melt spinning, energy costs are reduced and productivity is improved. Therefore, in order to perforate many base holes in one base, it is necessary to stabilize the discharge and thinning of each hole.

  In order to achieve this, it is important to reduce the diameter of the base hole and increase the land length (the length of the straight pipe portion equal to the diameter of the base hole). However, if the hole diameter is excessively small, clogging of the hole is likely to occur, so that the diameter is preferably 0.03 mm to 0.30 mm, more preferably 0.05 mm to 0.25 mm, and further preferably 0.08 mm to 0.20 mm. preferable. If the land length is excessively long, the pressure loss increases. Therefore, the L / D defined by the quotient obtained by dividing the land length by the hole diameter is preferably 0.5 or more and 3.0 or less, more preferably 0.8 or more and 2.5 or less. Preferably, it is 1.0 or more and 2.0 or less. In order to maintain uniformity, the number of holes in one die is preferably 50 holes or less, more preferably 40 holes or less, and even more preferably 20 holes or less. In addition, it is preferable that the introduction hole located immediately above the die hole is a straight hole having a diameter of 5 times or more the diameter of the die hole in terms of not increasing pressure loss. It is preferable to taper the connection part between the introduction hole and the base hole in order to suppress abnormal stagnation. However, the length of the taper part should be less than twice the land length without increasing pressure loss and stabilizing the streamline. This is preferable.

  The polymer discharged from the base hole passes through a heat retaining and cooling region and solidifies, and is then taken up by a roller (godet roller) that rotates at a constant speed. If the heat-retaining region is excessively long, the yarn forming property is deteriorated, so that it is preferably up to 200 mm from the base surface, and more preferably up to 100 mm. In the heat retaining region, it is possible to increase the ambient temperature by using a heating means, and the temperature range is preferably 100 ° C. or higher and 500 ° C. or lower from the viewpoint of improving the spinning property, and more preferably 200 ° C. or higher and 400 ° C. or lower. For the cooling, an inert gas, air, water vapor, or the like can be used. However, it is preferable to use an air flow that is jetted in parallel or in an annular shape from the viewpoint of reducing the environmental load.

  The take-up speed is preferably 50 m / min or more, more preferably 300 m / min or more, and further preferably 500 m / min or more in order to reduce productivity and single yarn fineness. Since the liquid crystalline polyester used in the present invention has a suitable spinnability at the spinning temperature, the take-up speed can be increased. Although the upper limit is not particularly limited, the liquid crystal polyester used in the present invention is about 2000 m / min from the viewpoint of spinnability.

  The spinning draft defined by the quotient obtained by dividing the take-off speed by the discharge linear speed is preferably 1 or more and 500 or less, more preferably 5 or more and 200 or less, and even more preferably 12 or more and 100 or less. Since the liquid crystalline polyester used in the present invention has suitable spinnability, the draft can be increased, which is advantageous for fineness.

  In melt spinning, it is preferable to add an oil agent between the cooling and solidification of the polymer and the winding to improve the handleability of the fiber. As the oil agent, known oil agents can be used, but it is more preferable to use an oil agent mainly composed of polysiloxane-based silicone oil that can withstand solid-phase polymerization at high temperatures.

  Winding can be carried out using a known winder to form a package such as pirn, cheese, corn, etc. However, it is not necessary to make the wrapping so that the roller does not come into contact with the surface of the package during winding. It is preferable in that it is not fibrillated.

  Next, in order to obtain the fiber of the present invention, it is necessary to increase ΔHm1, and in order to achieve this efficiently, it is preferable to solid-phase polymerize the fiber. Solid-phase polymerization can be processed in the form of a package, cake, tow (for example, on a metal net), or as a continuous thread between rollers, but the equipment can be simplified and produced. It is preferable to carry out in the form of a package from the viewpoint of improving the properties.

  When performing solid-phase polymerization in the form of a package, in order to increase the strength and elastic modulus and increase the fineness in the longitudinal direction of the fiber and the uniformity of strength, there is a technology that prevents remarkable fusion when the single fiber fineness is reduced. It becomes important.

  In order to prevent fusion, the winding density of the fiber package at the time of solid phase polymerization is important. In order to prevent winding collapse, the winding density is 0.01 g / cc or more, and in order to avoid fusion, winding is not necessary. The density is preferably less than 0.30 g / cc. Here, the winding density is a value calculated by Wf / Vf from the occupied volume Vf (cc) of the package and the weight Wf (g) of the fiber obtained from the outside dimensions of the package and the dimensions of the bobbin that is the core material. The smaller the winding density, the weaker the adhesion between the fibers in the package and the suppression of fusion, so 0.15 g / cc or less is preferable, and if the winding density is excessively small, the package collapses and is 0.03 g / cc or more. It is preferable. The occupied volume Vf is a value obtained by actually measuring the outer dimension of the package or by taking a photograph and measuring the outer dimension on the photograph and assuming that the package is rotationally symmetric. Wf is the fineness And a value calculated from the winding length, or a value measured by a weight difference before and after winding.

  When such a low winding density package is formed by winding in melt spinning, it is desirable to improve equipment productivity and production efficiency. On the other hand, a package wound by melt spinning is formed by rewinding. Is preferable because the winding tension can be reduced and the winding density can be further reduced. In the rewinding, the winding density can be reduced as the winding tension is reduced. Therefore, the winding tension is preferably 0.15 cN / dtex or less, and more preferably 0.10 cN / dtex or less.

  In order to reduce the winding density, the surface of the fiber package is wound in a non-contact state or wound by melt spinning without using a contact roller or the like normally used to adjust the package shape and stabilize the winding tension. It is also effective to wind the package directly with a winder controlled in speed without using a speed control roller. In these cases, in order to adjust the package shape, a method in which the distance (free length) from the contact point between the traverse guide and the fiber to the fiber package is within 10 mm is preferably used. Furthermore, it is also effective to reduce the winding density by setting the winding speed to 500 m / min or less, particularly 300 m / min or less. On the other hand, a higher rewinding speed is advantageous for productivity, and it is preferably 50 m / min or more, particularly preferably 100 m / min or more.

  Further, in order to form a stable package even in the case of low tension winding, the winding form is preferably a tapered end winding with both ends tapered. At this time, the taper angle is preferably 60 ° or less, and more preferably 45 ° or less. When the taper angle is small, the fiber package cannot be enlarged, and when long fibers are required, it is preferably 1 ° or more, and more preferably 5 ° or more. The taper angle referred to in the present invention is defined by the following equation. Furthermore, in winding, the traverse width is periodically swung with respect to time, whereby a package having excellent handling and unwinding properties can be obtained.

  Furthermore, the number of winds is also important for package formation. The number of winds referred to here is the number of times the spindle rotates during a half-reciprocation of the traverse, and is defined by the product of the time (minutes) of the traverse half-reciprocation and the spindle rotation speed (rpm). Indicates that the corner is small. The smaller the number of winds, the smaller the contact area between the fibers, which is advantageous for avoiding fusion. However, the higher the number of winds under the conditions such as low tension and no contact roll, which are preferable winding conditions in the present invention. Twill fall off at the end face and the swelling of the package can be reduced, and the package shape is improved. From these points, the wind number is preferably 2 or more and 20 or less, more preferably 5 or more and 15 or less.

  The bobbin used to form the fiber package may be of any cylindrical shape, and when wound as a fiber package, it is attached to a winder and rotated to wind the fiber and form a package. . In the solid-phase polymerization, the fiber package can be processed integrally with the bobbin, but the bobbin alone can be extracted from the fiber package for processing. When the treatment is carried out while being wound around the bobbin, the bobbin needs to withstand the solid phase polymerization temperature, and is preferably made of a metal such as aluminum, brass, iron or stainless steel. Further, in this case, it is preferable that the bobbin has a large number of holes because the polymerization reaction by-products can be removed quickly and solid phase polymerization can be performed efficiently. Further, when the bobbin is extracted from the fiber package and processed, it is preferable to attach an outer skin to the bobbin outer layer. In any case, it is preferable that a cushion material is wound around the outer layer of the bobbin, and the liquid crystalline polyester melt-spun fiber is wound thereon. The cushion material is preferably felt made of organic fiber or metal fiber, and the thickness is preferably 0.1 mm or more and 20 mm or less. The aforementioned outer skin can be substituted with the cushion material.

  The fiber weight of the fiber package may be any weight, but is preferably 0.01 kg or more and 10 kg or less in consideration of productivity. The yarn length is preferably in the range of 10,000 m to 2 million m.

  Moreover, in order to prevent the melt | fusion at the time of solid-phase polymerization, it is preferable embodiment to make an oil component adhere to the fiber surface. The adhesion of these components may be performed between melt spinning and winding, but in order to increase the adhesion efficiency, it is performed at the time of rewinding, or a small amount is adhered by melt spinning and further added at the time of rewinding. Is preferred.

  The oil adhering method may be a guide oiling method, but in order to uniformly adhere to fibers having a fine total fineness, adhesion by a metal or ceramic kiss roll (oiling roll) is preferable. As the oil component, it is better to have high heat resistance because it is not volatilized by high-temperature heat treatment in solid phase polymerization, and inorganic substances such as salt, talc, smectite, fluorine compounds, siloxane compounds (dimethylpolysiloxane, diphenylpolysiloxane, Methylphenyl polysiloxane and the like) and mixtures thereof are preferred. Of these, siloxane compounds are particularly preferred because they have an effect on slipperiness in addition to the effect of preventing fusion under solid weight.

  These components may be solid-coated or directly coated with oil, but emulsion coating is preferred for uniform coating while optimizing the amount of coating, and water emulsion is particularly preferred from the viewpoint of safety. Therefore, it is desirable that the component is water-soluble or easily form a water emulsion, and a mixed oil agent mainly composed of a water emulsion of dimethylpolysiloxane and a salt or water-swellable smectite added thereto is most preferable.

  The amount of the oil adhering to the fiber is preferably large in order to suppress fusion, and is preferably 0.5% by weight or more, and more preferably 1.0% by weight or more. On the other hand, if the amount is too large, the fiber deteriorates the sticky handling, and also deteriorates the process passability in the subsequent step, so that it is preferably 10.0% by weight or less, more preferably 8.0% by weight or less, and 6.0% by weight or less. Particularly preferred. In addition, the oil adhesion amount to a fiber refers to the value calculated | required by the method described in the Example.

  Solid-phase polymerization can be carried out in an inert gas atmosphere such as nitrogen, an oxygen-containing active gas atmosphere such as air, or under reduced pressure, but it can simplify equipment and prevent oxidation of fibers or deposits. Therefore, it is preferable to carry out in a nitrogen atmosphere. At this time, the atmosphere of the solid phase polymerization is preferably a low-humidity gas having a dew point of −40 ° C. or less.

  The solid phase polymerization temperature is preferably not lower than the melting point of the liquid crystalline polyester fiber subjected to solid phase polymerization at −60 ° C. It is preferable that the maximum temperature is less than Tm1 (° C.) in order to prevent fusion. By setting the temperature close to the melting point, solid phase polymerization proceeds rapidly, ΔHm1 increases, and strength and elastic modulus are improved. In addition, since the melting point of the liquid crystal polyester fiber increases with the progress of the solid phase polymerization, the solid phase polymerization temperature can be sequentially increased. Increasing the solid-phase polymerization temperature stepwise or continuously with respect to time is more preferable because it can prevent fusion and increase the time efficiency of solid-phase polymerization. However, also in this case, it is preferable that the maximum temperature achieved in the solid phase polymerization is Tm1-60 (° C.) or higher and less than Tm1 (° C.) of the fiber after heat treatment from the viewpoint of increasing the solid phase polymerization rate and preventing fusion. .

  The solid phase polymerization time is preferably 5 hours or more at the highest temperature and more preferably 10 hours or more in order to sufficiently increase ΔHm1 and reduce the peak half-value width at Tm1. The upper limit is not particularly limited, but the effect of increasing ΔHm1 and decreasing the peak half-value width is saturated with the elapsed time, so about 100 hours is sufficient.

  The package after the solid phase polymerization can be used as a product as it is, but it is preferable to rewind the package after the solid phase polymerization and increase the winding density again in order to increase the product transport efficiency. In unwinding after solid-phase polymerization, unraveling is important. In order to prevent the solid-phase polymerization package from collapsing due to unraveling, and to suppress fibrillation when peeling light fusion, the solid-phase polymerization package is rotated. It is preferable to unwind the yarn in the direction perpendicular to the rotation axis (fiber wrapping direction) by so-called pre-cutting, and it is further understood that the rotation of the solid-state polymerization package is not positively rotated but actively driven. This is preferable in that the tension during drought can be further reduced and fibrillation can be suppressed.

  It is a preferred embodiment to remove the oil from the fiber subjected to solid state polymerization. Although the effect is higher as the amount of adhesion of oil such as inorganic substances, fluorine-based compounds, and siloxane-based compounds increases for the suppression of fusion in solid-phase polymerization, if there is too much oil in the processes after solid-phase polymerization and weaving processes It is preferable to reduce the oil adhesion amount to the minimum necessary because it causes deterioration of process passability due to deposition on the guide and soot, and generation of defects due to mixing of the deposit into the product. For this reason, by removing the oil component adhering before solid-phase polymerization after solid-phase polymerization, it is possible to achieve both fusion suppression, improvement in uniformity in the longitudinal direction and improvement in process passability.

  The oil removal method is not particularly limited, and examples include a method of wiping with a cloth or paper while continuously running the fiber, but the oil is dissolved or dispersed in that the removal efficiency can be improved without giving a mechanical load to the fiber. A method in which the fiber is immersed in a liquid that can be formed is preferable. At this time, the fibers may be immersed in the liquid while running continuously, or the fibers may be immersed in the liquid in a package state. In the method of removing while continuously running, the removal can be performed uniformly in the longitudinal direction of the fiber, and the equipment can be simplified. The removal method in the package state is excellent in productivity because the processing amount per unit time increases.

  The liquid used for removal is preferably water in order to reduce the environmental load. The higher the temperature of the liquid, the higher the removal efficiency. The temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. However, when the temperature is too high, the evaporation of the liquid becomes remarkable, and therefore the boiling point of the liquid is preferably −10 ° C. or lower, more preferably the boiling point −20 ° C. or lower. Furthermore, addition of surfactants to liquids, liquid bubbles or ultrasonic vibrations, application of liquid flow, application of vibrations to fibers immersed in the liquid, etc. can increase the dissolution or dispersion rate of oil in the liquid. Is particularly preferable.

  Although the degree of oil removal is appropriately adjusted according to the purpose, it is preferable to leave oil to some extent to improve the processability and wear resistance of the fibers in the higher processing and weaving processes. It is also a preferred embodiment to apply a different kind of oil after removing most of the oil.

  The final oil adhesion amount to the fiber is preferably 0.1% by weight or more based on the fiber weight. In addition, the oil adhesion amount said by this invention refers to the value calculated | required by the method of an Example description. As the oil content increases, the effect of improving process passability and wear resistance increases, so 0.5% by weight or more is more preferable, and 1.0% by weight or more is more preferable. However, if too much oil is present, the adhesive strength between fibers will increase, running tension will become unstable, oil will accumulate on the guide and the process will deteriorate, and sometimes it will be mixed into the product and cause defects. It is preferably 10% by weight or less, more preferably 6% by weight or less, and further preferably 4% by weight or less. In this case, it is particularly preferable that the oil contains a polydimethylsiloxane compound for improving process passability and wear resistance. In the present invention, it is determined by the method described in the examples that the adhered oil contains a polysiloxane compound.

  The liquid crystalline polyester fiber of the present invention has high strength, high elastic modulus, high heat resistance, and high thermal dimensional stability, and has a reduced single fiber fineness and improved wear resistance. Widely used in fields such as civil engineering and construction materials, sports applications, protective clothing, rubber reinforcement materials, electrical materials (especially as tension members), acoustic materials, and general clothing. Effective applications include screen kites, filters, ropes, nets, fishnets, computer ribbons, printed circuit board base fabrics, paper canvases, air bags, airships, dome base fabrics, rider suits, fishing lines, various lines (Yachts, paragliders, balloons, kites), blind cords, support cords for screen doors, various cords for automobiles and aircraft, power transmission cords for electrical products and robots, etc. Examples of the monofilament used include a mesh fabric for a filter and a screen for printing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this. The various characteristics of the present invention were evaluated by the following methods.

(1) Weight average molecular weight in terms of polystyrene (molecular weight)
A mixed solvent of pentafluorophenol / chloroform = 35/65 (weight ratio) was used as a solvent, and the solution was dissolved so that the concentration of liquid crystal polyester was 0.04 to 0.08 weight / volume% to obtain a sample for GPC measurement. In addition, when there was an insoluble matter even after standing at room temperature for 24 hours, the mixture was left still for 24 hours, and the supernatant was used as a sample. This was measured using a GPC measuring apparatus manufactured by Waters, and the weight average molecular weight (Mw) was determined by polystyrene conversion.
Column: 2 Shodex K-806M, 1 K-802 Detector: Differential refractive index detector RI (type 2414)
Temperature: 23 ± 2 ° C
Flow rate: 0.8 mL / min Injection volume: 200 μL
(2) Tm1, Tm1 peak half width of liquid crystal polyester fiber, ΔHm1, Tc, ΔHc, Tm2, ΔHm2, melting point of liquid crystal polyester polymer Thermal analysis of the fiber was performed by DSC2920 manufactured by TA instruments, and differential calorimetry was performed from 50 ° C. The temperature of the endothermic peak observed when measured under a temperature rising condition of 20 ° C./min was Tm1 (° C.), and the peak half-value width (° C.) and heat of fusion (ΔHm1) (J / g) at Tm1 were measured.

  Subsequently, after observing Tm1, the temperature of Tm1 + 20 ° C. is maintained for 5 minutes, and the temperature of the exothermic peak observed when measured under a temperature drop condition of 20 ° C./min is defined as Tc (° C.). (ΔHc) (J / g) was measured. Subsequently, the mixture was cooled to 50 ° C., and the endothermic peak observed when the temperature was again measured at 20 ° C./min was defined as Tm2, and the heat of fusion (ΔHm2) (J / g) at Tm2 was measured.

  In addition, about the liquid crystalline polyester polymer shown in the reference example, after observing Tm1, it was held at a temperature of Tm1 + 20 ° C. for 5 minutes, then cooled to 50 ° C. under a temperature decreasing condition of 20 ° C./minute, and again increased to 20 ° C./minute. The endothermic peak observed when measured under temperature conditions was defined as Tm2, and Tm2 was defined as the melting point of the polymer.

(3) Single fiber fineness and fineness variation rate 100 m of fiber was removed with a measuring machine, the weight (g) was multiplied by 100, and 10 measurements per level were performed, and the average value was defined as fineness (dtex). . The quotient obtained by dividing this by the number of filaments was defined as the single fiber fineness (dtex). The fineness variation rate was calculated by the following equation using the larger one of the absolute values of the difference between the maximum value and the minimum value from the average value of 10 finenesses.
Fineness fluctuation rate (%) = ((| maximum value or minimum value−average value | / average value) × 100)
(4) Strength, elongation, elastic modulus, and strength fluctuation rate According to the method described in JIS L1013: 1999, using Tensilon UCT-100 manufactured by Orientec Co., Ltd. under the conditions of a sample length of 100 mm and a tensile speed of 50 mm / min. The measurement was performed 10 times per average, and the average value was defined as strength (cN), strength (cN / dtex), elongation (%), and elastic modulus (cN / dtex). The strength fluctuation rate was calculated by the following formula using the larger one of the absolute values of the differences between the maximum and minimum values from the average value of 10 strengths.
Strong fluctuation rate (%) = ((| maximum or minimum value−average value | / average value) × 100)
(5) Thermal expansion coefficient At 50 ° C when TMA-50 manufactured by Shimadzu Corporation was used and a processing load of 0.03 cN / dtex was applied in the fiber axis direction and the temperature was increased from 40 ° C to 250 ° C at a rate of 5 ° C / min. The sample length L0 and the sample length L1 at 100 ° C. were used for calculation according to the following formula.
Thermal expansion coefficient (ppm / ° C.) = ((L0−L1) / (L0 × 50)) × 10 ⁶
(6) Compression modulus in the direction perpendicular to the fiber axis (compression modulus)
Place a single fiber on a highly rigid stage such as ceramic, and apply a compression load at a constant test speed using the indenter in the diameter direction under the following conditions with the side of the indenter approximately parallel to the fiber. After obtaining the load-displacement curve, the compression elastic modulus in the direction perpendicular to the fiber axis was calculated from the following equation.

  In the measurement, in order to correct the deformation amount of the device system, a load-displacement curve is obtained without placing the sample, and this is approximated by a straight line to calculate the deformation amount of the device with respect to the load. -From the displacement of each data point when the displacement curve was measured, the amount of deformation of the apparatus with respect to the load was subtracted to obtain the displacement of the sample itself, which was used for the following calculation.

  In the calculation, the compression elastic modulus was calculated using the load and displacement at two points where linearity is established in the load-displacement curve. The point on the low load side is a point where the load is about 30 mN because there is a possibility that the indenter does not hit the entire surface of the sample at the initial stage when the load is applied. However, when the low load point determined here is in the non-linear region, a straight line is drawn on the low load side along the load-displacement curve so as to pass the yield point, and the deviation between the straight line and the displacement is within 0.1 μm. The minimum load point is The high load side was a point with a load of about 100 mN. When the point on the high load side exceeds the yield point load, a straight line is drawn on the high load side along the load-displacement curve so as to pass the point on the low load side, and the displacement deviation from that line is zero. The point of maximum load within 1 μm was taken as the point on the high load side. In addition, l in the following formula is calculated as 500 μm, and the single fiber radius is a value obtained by measuring the diameter of the sample 10 times using an optical microscope before the test and halving the average diameter obtained by averaging this. Was used. Further, the load-displacement curve was measured 5 times for the sample 1 level, the compression elastic modulus was also calculated 5 times, and the average of these was taken as the compression elastic modulus.

Apparatus: Instron super precision material testing machine Model 5848
Indenter: Diamond flat indenter (square with a side of 500 μm)
Test speed: 50 μm / min Sampling speed: 0.1 second Data processing system: “Merlin” manufactured by Instron
Measurement atmosphere: At room temperature in air (23 ± 2 ° C., 50 ± 5% RH)
(7) Peak half-width (Δ2θ) in wide-angle X-ray diffraction
The fiber was cut into 4 cm, 20 mg of the fiber was weighed and used as a sample. The measurement was performed in the equator direction with respect to the fiber axis direction, and the conditions were as follows. At this time, the half width (Δ2θ) of the peak observed at 2θ = 18 to 22 ° was measured.
X-ray generator: Rigaku Denki 4036A2 type X-ray source: CuKα ray (using Ni filter)
Output: 40kV-20mA
Goniometer: Rigaku Denki 2155D type slit: 2mmφ-1 ° -1 °
Detector: Scintillation counter counting recording device: RAD-C type measurement range manufactured by Rigaku Corporation: 2θ = 5-60 °
Step: 0.05 °
Integration time: 2 seconds (8) Abrasion resistance A fiber loaded with a load of 2.45 cN / dtex (2.5 g weight / dtex) is hung vertically and is hard with a diameter of 3.8 mm so as to be perpendicular to the fiber. Press the chrome-satin-finished metal rod guide (bar guide manufactured by Yuasa Yindo Kogyo Co., Ltd.) at a contact angle of 2.7 °, and rub the guide in the fiber axis direction at a stroke length of 30 mm and a stroke speed of 600 times / min. Observe and measure the number of seconds until the occurrence of white powder or fibrils is confirmed on the rod guide or on the fiber surface, and obtain the average value of 5 times excluding the maximum and minimum values from the 7 measurements. Wear resistance. The abrasion resistance was evaluated by the same test method for multifilaments.

(9) Birefringence (Δn)
Using a polarizing microscope (BLY-2 manufactured by OLYMPUS), measurement was performed 5 times per one sample level by the compensator method, and the average value was obtained.

(10) Judgment of oil adhesion amount and polysiloxane compound adhesion 100 mg or more of fibers were collected and weighed after drying for 10 minutes at 60 ° C. (W0), and water more than 100 times the fiber weight. The fiber was immersed in a solution containing 2.0% by weight of sodium dodecylbenzenesulfonate added to the fiber, ultrasonically washed at room temperature for 20 minutes, the washed fiber was washed with water, and dried at 60 ° C. for 10 minutes. The weight after the measurement was measured (W1), and the oil adhesion amount was calculated by the following formula.
(Amount of oil adhering (weight%)) = (W0−W1) × 100 / W1
In addition, the determination of polysiloxane compound adhesion was obtained by collecting a solution after ultrasonic cleaning, performing IR measurement, and determining the polysiloxane against the peak intensity of 1150 to 1250 cm ⁻¹ derived from the sulfonic acid group of sodium dodecylbenzenesulfonate. If the derived peak intensity of 1050 to 1150 cm ⁻¹ was 0.1 times or more, it was judged that the polysiloxane adhered to the fiber.

(11) Running tension and running stress Measured using a tension meter (MODEL TTM-101) manufactured by Toray Engineering. In addition, a tension meter capable of measuring a full scale of 5 g and an accuracy of 0.01 g was used for the extremely low tension. The measured traveling tension was converted into a unit and divided by the fineness of the treated fiber to obtain the traveling stress as a unit of cN / dtex.

(12) Evaluation of weaving properties and fabric characteristics Using a rapier loom with 13 dtex polyester monofilament for warp, weaving density, weft 100 weighs per inch (2.54 cm), and weaving speed 100 times / min. Weaved. At this time, the process passability was evaluated from the fibril and scum accumulation on the yarn feeder (ceramic guide) in the trial weaving with a width of 180 cm and a weaving length of 100 cm, and the weaving property was evaluated from the number of stops due to yarn breakage. The quality of the fabric was evaluated from the number of mixed fibrils and scum. The criteria for each are described below. The thickness of the woven fabric was measured using a dial thickness gauge manufactured by Peacock.

<Process passability>
Even after weaving, no fibril or scum accumulation is observed; excellent (◎)
Fibrils and scum are observed after weaving, but there is no hindrance to fiber running; good (○)
Fibrils and scum are observed after weaving, and fiber running tension increases; reject (△)
Fibrils and scum were observed during weaving, and trial weaving was stopped; defective (×)
Weaving <Weaving>
Stop 0 times; Excellent (◎), Stop 1 to 2 times; Pass (○)
Stop 3 to 5 times; Fail (△), Stop 6 times or more; Defect (x)
In addition, the quality of the fabric was evaluated from the number of fibrils mixed in the fabric. The criteria are as follows.

<Textile grade>
0; Excellent (◎), 1-2; Good (◯), 3-5; Fail (△), 6 or more; Poor (x)
Reference example 1
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 870 parts by weight of p-hydroxybenzoic acid, 327 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid Then, 1433 parts by weight of acetic anhydride (1.08 equivalent of the total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 330 degreeC in 4 hours.

The polymerization temperature was maintained at 330 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference example 2
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 829 parts by weight of p-hydroxybenzoic acid, 570 parts by weight of 4,4′-dihydroxybiphenyl, 374 parts by weight of terephthalic acid, 124 parts by weight of isophthalic acid, and 1337 parts by weight of acetic anhydride 1 part (1.08 mole equivalent of total phenolic hydroxyl groups) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and the temperature was raised from room temperature to 145 ° C. over 30 minutes while stirring in a nitrogen gas atmosphere. The reaction was carried out at 2 ° C. for 2 hours. Then, it heated up to 360 degreeC in 4 hours.

The polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, and the reaction was continued for another 5 minutes. When the torque reached 15 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference example 3
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 907 parts by weight of p-hydroxybenzoic acid, 457 parts by weight of 6-hydroxy-2-naphthoic acid, and 946 parts by weight of acetic anhydride (1.03 mol of the total phenolic hydroxyl group) Equivalent) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, and then the reaction was carried out at 145 ° C. for 2 hours. Then, it heated up to 325 degreeC in 4 hours.

The polymerization temperature was maintained at 325 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference example 4
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 808 parts by weight of p-hydroxybenzoic acid, 411 parts by weight of 4,4′-dihydroxybiphenyl, 104 parts by weight of hydroquinone, 314 parts by weight of terephthalic acid, 209 parts by weight of isophthalic acid Then, 1364 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) was charged, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 300 degreeC in 4 hours.

The polymerization temperature was maintained at 300 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, and the reaction was continued for another 20 minutes. When the torque reached 15 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 5
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 323 parts by weight of p-hydroxybenzoic acid, 436 parts by weight of 4,4′-dihydroxybiphenyl, 109 parts by weight of hydroquinone, 359 parts by weight of terephthalic acid, 194 parts by weight of isophthalic acid Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 325 degreeC in 4 hours.

The polymerization temperature was maintained at 325 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 6
895 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4′-dihydroxybiphenyl, 40 parts by weight of hydroquinone, 135 parts by weight of terephthalic acid, 75 parts by weight of isophthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillation tube Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 365 degreeC in 4 hours.

The polymerization temperature was maintained at 365 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 7
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 671 parts by weight of p-hydroxybenzoic acid, 235 parts by weight of 4,4′-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 224 parts by weight of terephthalic acid, 120 parts by weight of isophthalic acid Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 340 degreeC in 4 hours.

The polymerization temperature was maintained at 340 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, and the reaction was continued for another 20 minutes. When the torque reached 15 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 8
In a 5 L reaction vessel equipped with a stirring blade and a distillation pipe, 671 parts by weight of p-hydroxybenzoic acid, 335 parts by weight of 4,4′-dihydroxybiphenyl, 30 parts by weight of hydroquinone, 224 parts by weight of terephthalic acid, 120 parts by weight of isophthalic acid Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 305 degreeC in 4 hours.

The polymerization temperature was maintained at 305 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 9
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 671 parts by weight of p-hydroxybenzoic acid, 268 parts by weight of 4,4′-dihydroxybiphenyl, 69 parts by weight of hydroquinone, 314 parts by weight of terephthalic acid, 30 parts by weight of isophthalic acid Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 355 degreeC in 4 hours.

The polymerization temperature was maintained at 355 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, and the reaction was continued for another 20 minutes. When the torque reached 15 kgcm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

Reference Example 10
In a 5 L reaction vessel equipped with a stirring blade and a distillation pipe, 671 parts by weight of p-hydroxybenzoic acid, 268 parts by weight of 4,4′-dihydroxybiphenyl, 69 parts by weight of hydroquinone, 150 parts by weight of terephthalic acid, 194 parts by weight of isophthalic acid Then, 1011 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) was added, and the temperature was raised from room temperature to 145 ° C. over 30 minutes with stirring in a nitrogen gas atmosphere, followed by reaction at 145 ° C. for 2 hours. Then, it heated up to 310 degreeC in 4 hours.

The polymerization temperature was maintained at 310 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.5 hours, the reaction was continued for another 20 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  The characteristics of the liquid crystalline polyester obtained in Reference Examples 1 to 10 are shown in Table 1. Each resin was heated and heated in a nitrogen atmosphere on a hot stage, and when the transmitted light of the sample was observed under polarized light, optical anisotropy (liquid crystallinity) was confirmed. The melt viscosity was measured using a Koka flow tester at a melting point of + 10 ° C. and a shear rate of 1000 / s.

Example 1
After vacuum drying at 160 ° C. for 12 hours using the liquid crystalline polyester of Reference Example 1, it was melt extruded with a φ15 mm single-screw extruder (heater temperature 290 to 340 ° C.) manufactured by Osaka Seiki Co., Ltd. and measured with a gear pump. However, the polymer was supplied to the spinning pack. The spinning temperature from the extruder to the spinning pack at this time was 345 ° C. In the spinning pack, the polymer is filtered using a metal nonwoven fabric filter (WLF-10 manufactured by Watanabe Yoshikazu Co., Ltd.), and the discharge rate is 3.0 g / min from a die having five holes with a hole diameter of 0.13 mm and a land length of 0.26 mm ( The polymer was discharged at a rate of 0.6 g / min per single hole. The discharged polymer is allowed to pass through a 40 mm heat-retaining region, and then cooled and solidified from the outside of the yarn with an annular cooling air. Thereafter, an oil containing polydimethylsiloxane as a main component is applied, and all the 5 filaments are 1200 m / min. I took it to 1 godet roll. The spinning draft at this time is 32. After passing this through the second godet roll at the same speed, four of the five filaments are sucked with a suction gun, and the remaining one is a pirn winder through the dancer arm (no contact roll contacting the winding package). Was wound up into the shape of a pan. During the winding time of about 100 minutes, yarn breakage did not occur and the yarn making property was good. The properties of the obtained spun fiber are shown in Table 2.

A winding machine (ET-68S controlled winding by Kozu Seisakusho Co., Ltd.) that unwinds fibers from the spun fiber package in the longitudinal direction (perpendicular to the fiber circulation direction) and keeps the speed constant without using a speed control roller. Machine) at 200 m / min. In addition, as the core material for rewinding, a stainless steel perforated bobbin wound with Kevlar felt (weight per unit: 280 g / m ² , thickness 1.5 mm), the tension at the time of rewinding was 0.10 cN / dtex, and the winding amount was It was 120,000 m, that is, 0.06 kg. Furthermore, the package form is a taper end winding with a taper angle of 20 °, the traverse width is always oscillated by modifying the taper width adjusting mechanism, no contact roll is used, and the traverse guide and fiber contact point is 5 mm from the fiber package. did. Further, polydimethylsiloxane (SH200 manufactured by Toray Dow Corning Co., Ltd.) was used as an oil agent with a 5.0% by weight water emulsion, and lubrication was performed using a satin finish stainless steel roll before the winder. The wound density of the package wound up in this way was 0.14 g / cc, and the oil adhesion amount was 4.4% by weight.

  Using a closed oven, the temperature was raised from room temperature to 240 ° C. in about 30 minutes, held at 240 ° C. for 3 hours, then raised to 295 ° C. at 4 ° C./hour, and further at 295 ° C. for 15 hours. Solid state polymerization was performed under the condition of maintaining the time. The atmosphere was supplied with dehumidified nitrogen at a flow rate of 25 NL / min, and exhausted from the exhaust port so that the interior was not pressurized.

  The solid phase polymerization package thus obtained is attached to a feeding device that can be rotated by an inverter motor, and a winder (ET type manufactured by Kozu Seisakusho Co., Ltd.) is fed while feeding the fibers in the transverse direction (fiber circulation direction) at a yarn feeding speed of about 200 m / min. As a result, it was possible to unwind the entire amount without breaking the yarn, although oil was adhered to the guide. While further unwinding this fiber, a washing device in which a water bath having a bath length of 1000 mm was filled with water at room temperature (25 ° C.) and bubbled inside the water bath using a bubble generator installed in the water bath was 100 m / min. Passed at speed. In addition, a smoothing agent composed mainly of a polyether compound and a water emulsion of an emulsifier mainly composed of lauryl alcohol (emulsion concentration 4% by weight) are used as finishing oils, and a stainless steel roll with a satin finish is used before the winder. Refueling was performed (Table 3).

  The physical properties of the obtained liquid crystal polyester fiber are shown in Table 4 (fiber physical properties after solid weight). It has a high molecular weight, high strength, high elastic modulus, high melting point, high ΔHm1, which is a characteristic of solid-state polymerized liquid crystal polyester fiber, and has a fineness variation rate and strength variation rate that are small in the longitudinal direction with a fineness of 5.1 dtex. It can be seen that the uniformity is also excellent. The liquid crystalline polyester fiber had a thermal expansion coefficient of -7 ppm / ° C. and excellent thermal dimensional stability. Further, Δn was 0.35 and had a high orientation.

  Trial fabric evaluation was performed using this liquid crystal polyester fiber. Although the result is also described in Table 4, the process-passing property and weaving property are excellent, and a thin woven fabric was obtained. One fibril was found in the fabric, but the quality was good. Thus, it can be seen that a finely-solidified solid-phase polymerized fiber made of a liquid crystal polyester having a specific composition of the present invention is excellent in process passability, weaving property, and textile quality.

Examples 2-4
Melt spinning was carried out in the same manner as in Example 1 except that the discharge amount, the nozzle hole diameter, the land length, and the spinning speed were set as shown in Table 2. In Example 2, a 100 mm heating cylinder (insulating region 100 mm) was provided under the base, and this temperature was 200 ° C. In Example 2, thread breakage occurred once at the start of winding, but when it was wound again, winding for 100 minutes was possible. In Examples 3 and 4, winding for 240 minutes was performed, but the yarn forming property was good.

  Rewinding was performed in the same manner as in Example 1 except that the rewinding speed and the winding amount were the conditions shown in Table 3, and solid phase polymerization and unwinding were performed. The winding tension, winding density, and oil adhesion amount at this time are as shown in Table 3. In Example 2, thread breakage occurred once, but the entire amount could be wound. The unwound fiber was washed and applied with a finishing oil in the same manner as in Example 1. Table 4 shows the physical properties of the fibers thus obtained. By using the liquid crystalline polyester of Reference Example 1 and adjusting the spinning conditions, a uniform fiber having a fine single yarn fineness and a small fineness variation rate is obtained, and ΔHm1 / ΔHm2 is 3.0 or more and the peak half width at Tm1 is It can be seen that when the temperature is less than 15 ° C., a fiber having high strength and elastic modulus, excellent thermal dimensional stability, and excellent wear resistance can be obtained.

  Table 4 also shows the results of evaluation of trial fabrics. In Example 2, although fibrils were accumulated near the yarn feeder, the process passing property was good, the weaving property was good even though one stop occurred during weaving, and the fabric quality was good even though there were two fibrils in the fabric. In Examples 3 and 4, both the process passability and the weaving property were excellent, the number of fibrils in the fabric was one, and the quality of the fabric was also good. Thus, it can be seen that by using the liquid crystal polyester fiber of the present invention, weaving property is good, the fabric thickness can be reduced, and the fabric quality is also good.

Examples 5 and 6
Except for setting the discharge amount and the number of nozzle holes as shown in Table 2, melt spinning was performed under the same conditions as in Example 1, and 10 filaments were rolled up to obtain a spun fiber (Example 5). Also, melt spinning was performed under the same conditions as in Example 1 except that the discharge amount and the number of nozzle holes were set as shown in Table 2, and 36 filaments were rolled up to obtain a spun fiber (Example 6). Table 2 shows the physical properties of the obtained fiber. The spinning property was good, and it was possible to wind up about 100 minutes. This was wound up in the same manner as in Example 1 except that the winding amount was the conditions shown in Table 3, and solid phase polymerization and unwinding were performed. The winding tension, winding density, and oil adhesion amount at this time are as shown in Table 3. Next, the entire package after unwinding was immersed in an ultrasonic cleaner filled with a solution obtained by adding 0.05% by volume of a surfactant to warm water at 40 ° C., and subjected to ultrasonic cleaning for 15 minutes 6 times. . Thereafter, the fibers were unwound in a state where the package was not dried, and washing and finishing oil application were performed in the same manner as in Example 1. Table 4 shows the physical properties of the fibers thus obtained. It can be seen that even if it is a multifilament, it is possible to obtain a uniform fiber having a small single yarn fineness and a small variation in fineness, a fiber having high strength and elastic modulus, and excellent wear resistance.

  Table 4 shows the results of evaluation of the test fabric using this fiber. The process-passing property and weaving property were both excellent, the number of fibrils in the fabric was two, and the fabric quality was also good.

  Thus, it can be seen that the solid-phase polymerized fiber made of the liquid crystalline polyester having the specific composition of the present invention is excellent in process passability, weaving property, and textile quality even with a multifilament.

Comparative Example 1
Using the liquid crystalline polyester of Reference Example 3, melt spinning was performed in the same manner as in Example 3 except that the spinning temperature was 325 ° C. The spinning property was good, and it was possible to wind up for 200 minutes.

  This was rewound by the same method as in Example 3 except that the final reached temperature of solid phase polymerization was set to the conditions shown in Table 3, and solid phase polymerization, unraveling, and washing were performed. The winding tension, winding density, and oil adhesion amount at this time are as shown in Table 3. The obtained fiber physical properties are listed in Table 4. It can be seen that the abrasion resistance is as bad as 2 seconds. From this, the liquid crystalline polyester of Reference Example 3 provides fibers having excellent properties in terms of single yarn fineness, ΔHm1 / ΔHm2, peak half width and strength at Tm1, and modulus of elasticity. It can be said that it is inferior.

  Table 4 shows the results of evaluation of the test fabric using this fiber. Although the thickness of the woven fabric can be reduced, fibrils were accumulated at the yarn feeder, and 6 stops were generated during weaving. Although weaving was only possible with a weaving length of about 30 cm, 10 or more fibrils were present, and the quality of the fabric was poor.

  Thus, it can be seen that the liquid crystalline polyester solid-phase-polymerized fibers that do not satisfy the composition of the present invention are inferior in wear resistance or inferior in process passability, weaving property and textile quality.

Comparative Example 2
The spun fiber obtained in Example 1 was evaluated as a liquid crystal polyester fiber without performing solid phase polymerization. Although it is described in Table 4 as the fiber physical properties subjected to the test weaving, it is excellent in single yarn fineness and fineness fluctuation rate, but has low strength and elastic modulus, low Tm1 and poor heat resistance, and a thermal expansion coefficient of -21 ppm. / ° C. and poor thermal dimensional stability. From these facts, the liquid crystal polyester fiber of Reference Example 1 is used, and even if the single yarn fineness is thin, even if the fineness variation rate is small, ΔHm1 / ΔHm2 is less than 3.0 and the peak half-value width of Tm1 is 15 ° C. or more. It can be said that it is not attractive.

  Trial weave evaluation was attempted using this fiber in the same manner as in Example 1. However, the yarn was broken when entering the loom, and weaving was impossible. Even the liquid crystalline polyester of the specific composition of the present invention cannot be woven because it has low strength and elongation unless it is subjected to solid phase polymerization.

Comparative Example 3
When melt spinning was performed in the same manner as in Example 1, the take-up bobbin was a stainless-made perforated bobbin, and was wound directly on this by 60,000 m. Table 3 shows the taper angle, wind number, winding tension, and winding density in this winding. Solid phase polymerization was performed in the same manner as in Example 1 without rewinding this. When the obtained solid phase polymerization package was unwound by the same method as in Example 1, yarn breakage frequently occurred at a unwinding speed of 200 m / min, and yarn breakage occurred frequently even at 50 m / min. It was.

  The characteristics of the obtained fiber are shown in Table 4. Although the characteristics of the liquid crystal polyester fiber subjected to solid phase polymerization such as high molecular weight, high melting point, and high ΔHm1 are expressed, the fluctuation rate of fineness due to fusion at the time of solid weight It can be seen that the increase in strength, the rate of change in strength greatly increases, the uniformity in the longitudinal direction deteriorates, and the values of strength and elastic modulus also decrease.

  Trial weaving was carried out in the same manner as in Example 1 using the obtained solid fiber after unwinding. The results are shown in Table 4. Since fibrils were accumulated at the yarn feeder and the stop was generated six times during weaving, the trial weaving was stopped halfway. Although weaving was only possible with a weaving length of about 5 cm, 10 or more fibrils were present, and the quality of the fabric was poor.

  Thus, even in the case of the solid phase polymerized fiber of the liquid crystalline polyester satisfying the composition of the present invention, when the longitudinal uniformity is inferior, the strength is low, and the abrasion resistance is inferior, so the process passability, weaving property, textile quality It turns out that it is inferior to.

Comparative Example 4
Using the liquid crystalline polyester of Reference Example 2, melt spinning was performed in the same manner as in Example 3 except that the spinning temperature was 370 ° C. However, the yarn breakage occurred about 1 minute after the start of winding, and after that, the fiber could not be wound, so that no fiber was obtained. It can be said that the liquid crystalline polyester of Reference Example 2 has difficulty in obtaining fibers with a fine single yarn fineness due to its resin characteristics.

Comparative Example 5
According to Comparative Example 8 of Patent Document 3, except that a nozzle having one nozzle hole having a discharge hole diameter of 0.5 mm and a land length of 0.5 mm is used, and the discharge amount and spinning speed are set to the conditions shown in Table 5. Melt spinning was performed in the same manner as in Example 1. After the start of winding, thread breakage occurred twice and the yarn-making property was poor (Table 5). This was rolled back in the same manner as in Example 1 except that the taper angle and the winding amount were changed (Table 6). Since it was found that the solid-phase polymerization did not sufficiently increase in strength under the same conditions as in Example 1 (about 16 cN / dtex), it was treated at the highest temperature for 45 hours. The results of unraveling the obtained solid phase polymerization package by the same method as in Example 1 are also shown in Table 6. In Comparative Example 5, two yarn breaks occurred. The unwound fiber was washed and applied with a finishing oil in the same manner as in Example 1. The physical properties of the fibers thus obtained are shown in Table 7. It can be seen that the single fiber fineness is large and the strength fluctuation rate is also large. It can also be seen that the wear resistance is inferior due to the large fluctuation rate of strength.

  Using this fiber, trial weaving was performed in the same manner as in Example 1. The results are also shown in Table 7. As a result, fibrils accumulated at the yarn feeder and the tension increased, and there were four stops in weaving. Moreover, five fibrils were recognized also in the textile fabric, and it failed.

  As described above, even in the case of the solid-phase polymerized fiber made of the liquid crystal polyester having the specific composition of the present invention, it is difficult to improve the uniformity in the longitudinal direction when the single fiber fineness is large, and the process passability, weaving property, and textile quality are inferior. I understand that.

Examples 7-13
Using the liquid crystalline polyesters of Reference Examples 4 to 10, melt spinning was performed in the same manner as in Example 3 except that the spinning temperature was set as shown in Table 5. In Example 9, although thread breakage occurred once, it did not occur in other cases, and the yarn-making property was good. The properties of the obtained fiber are shown in Table 5.

  These fibers were rewound by the same method as in Example 1 except that the taper angle and the winding amount were set to the conditions shown in Table 6, and the same as in Example 1 except that the maximum reached temperature was set to the conditions described in Table 6. Solid state polymerization and unwinding were carried out by this method. No thread breakage occurred during unwinding. Thereafter, washing and finishing oil application were performed in the same manner as in Example 1 (Table 6).

  The obtained fiber properties are listed in Table 7. Even when the liquid crystal polyesters of Reference Examples 4 to 10 were used, uniform fibers having a small single yarn fineness and a small variation in fineness were obtained, and ΔHm1 / ΔHm2 was 3 It can be seen that a fiber having high strength and elastic modulus and excellent thermal dimensional stability and wear resistance can be obtained when the peak half-width of Tm1 is less than 15 ° C.

  Using these fibers, trial weaving was performed in the same manner as in Example 1. The results are also shown in Table 7, and the process passability, weaving property and fabric quality were excellent or good.

  Thus, it can be seen that the solid-phase polymerized fiber made of the liquid crystalline polyester having a specific composition of the present invention is excellent in process passability, weaving property and textile quality even if the composition ratio is different.

Claims (5)

Following structural units (I), (II), (III), (IV) and a liquid crystal polyester consisting of (V), meets the following conditions 1 to 4, structural units (I) is a structural unit (I), 40 to 85 mol% with respect to the sum of (II) and (III), structural unit (II) is 60 to 90 mol% with respect to the sum of structural units (II) and (III), (IV) is 40-95 mol% with respect to the sum total of structural unit (IV) and (V), The liquid crystalline polyester fiber characterized by the above-mentioned.

Condition 1. In differential calorimetry, the heat of fusion (ΔHm1) at the endothermic peak (Tm1) observed when measured under the temperature rising condition from 50 ° C. to 20 ° C./min is held at a temperature of Tm1 + 20 ° C. for 5 minutes after the observation of Tm1. Then, the temperature is once cooled to 50 ° C. under a temperature lowering condition of 20 ° C./min, and 3 times the heat of fusion (ΔHm2) in the endothermic peak (Tm2) observed when measured again under the temperature rising condition of 20 ° C./min. More than 0 times.
Condition 2. The peak half-width at Tm1 is less than 15 ° C.
Condition 3. Single fiber fineness is 18.0 dtex or less.
Condition 4. The strength is 14.0 cN / dtex or more and the elastic modulus is 600 cN / dtex or more. Polysiloxane compound are attached to the fibers, the weight of the deposit with respect to the fiber 0.1 wt% or more, liquid crystal polyester fiber according to claim 1 Symbol placement is equal to or less than 10.0 wt%. The liquid crystal polyester fiber according to claim 1 or 2 , wherein the fineness variation rate is 30% or less and the strength variation rate is 20% or less. Claim 1-3 printing screen gauze comprising a liquid crystal polyester fiber according to any one. A mesh fabric for a filter comprising the liquid crystalline polyester fiber according to any one of claims 1 to 3 .