JP2009052150A - Fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber improving fluidity in a spinning process, reducing the spinning temperature with little yarn unevenness and improving the modulus of elasticity based on birefringence of the fiber, that is, to provide the fiber having low molecular orientation though with the high modulus of elasticity by using a dendritic polyester having suppressed entanglement of a matrix polymer with the molecular chain and hardly inhibiting the extension and deformation in the spinning process as opposed to a conventional polyester. <P>SOLUTION: The fiber includes a polymer blend obtained by blending 0.1-10 wt.% of dendritic polyester having a structural unit composed of an aromatic oxycarbonyl unit (P), an aromatic and aliphatic dioxy unit (Q) and an aromatic dicarbonyl unit (R) and a tri- or a higher functional organic residue (B) and having the content of B within the range of 7.5-50 mol% based on the total monomer constituting the dendritic polyester in a thermoplastic matrix polymer. The fiber has a Uster unevenness of the fiber of 0.1-5%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fiber comprising a polymer blend obtained by blending a dendritic polyester with a matrix polymer.

  Fibers using thermoplastic polymers such as polyester and polyamide are widely used, and the industrial value is extremely high. And these manufacturing methods employ | adopt melt spinning which extrudes from a thin nozzle | cap | die after melt | dissolving a polymer. At this time, the spinning temperature in melt spinning is determined by the melting point and melt viscosity of the polymer, but even when the melting point is the same, when spinning a high viscosity polymer, it is necessary to set a higher spinning temperature than in the case of a low viscosity polymer. There is. However, when the temperature is excessively high, decomposition of the polymer itself is promoted. In addition, in order to add functionality to the fiber, the function-added component is spun simultaneously. If the heat-resistant component of this function-added component is low, decomposition and accompanying gas may be generated. For this reason, in particular, when spinning a high viscosity polymer or simultaneously spinning a functional addition component having low heat resistance, a technique for improving the fluidity of the polymer and lowering the spinning temperature as much as possible is important.

  For this reason, various thinning agents may be used, but there have been few successful examples to date. Of particular interest among conventional techniques is an example in which a hyperbranched polymer (hyperbranched polymer) is added to nylon (Patent Document 1). Here, it is described that by adding a hyperbranched polymer that is non-reactive with the matrix polymer to the matrix polymer, the molecular weight reduction is less than 7% and the fluidity is improved as compared with the case where the matrix polymer is not added. However, since the branch structure portion (D) that is the main chain of the hyperbranched polymer is actually aliphatic (in the examples, derived from ε-caprolactam), the flexibility is extremely high. For this reason, even if the hyperbranched polymer and the matrix polymer are non-reactive, there is a possibility that many so-called molecular chains are entangled between the hyperbranched polymer main chain part and the matrix polymer main chain part. This is not a big problem because the amount of deformation is small in extrusion processing of resin and shear deformation is dominant, but it causes serious problems especially when accompanied by large elongation deformation such as spinning. was there. That is, the degree of entanglement of the molecular chains is increased, so that the smooth elongation deformation of the matrix polymer molecular chains is hindered, and the spinnability is remarkably deteriorated. In some cases, the elastic behavior of the polymer becomes remarkable and the spinning becomes impossible. there were. In addition, even when spinning is not possible, large-scale fluctuations (spots) occur in the elongation deformation of the spinning line, resulting in excessive thread fine spots, and there are cases where practical fibers cannot be obtained. In particular, when a high-viscosity polymer or a high-molecular-weight polymer is used as the matrix polymer, or when the fineness spinning or the spinning speed is increased, this tendency is remarkable.

For this reason, there has been a demand for hyperbranched polymers suitable for spinning and fibers, and fibers with small yarn spots to which they are added.
JP-T-2005-513186 (page 6-12)

  Unlike conventional systems, the use of dendritic polyester, which prevents entanglement between the matrix polymer and the molecular chain and does not hinder elongation deformation during the spinning process, improves fluidity during the spinning process and lowers the spinning temperature. At the same time, the present invention provides a fiber having a small molecular orientation and a small molecular orientation while improving the elastic modulus per birefringence of the fiber, that is, having a high elastic modulus.

The above object is achieved by the following means.
(1) including a structural unit composed of an aromatic oxycarbonyl unit (P), an aromatic and aliphatic dioxy unit (Q), and an aromatic dicarbonyl unit (R) and a trifunctional or higher functional organic residue (B) In addition, 0.1 to 10 wt% of a dendritic polyester having a B content in a range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester was blended with a thermoplastic matrix polymer. A fiber comprising a polymer blend, wherein the fiber has 0.1-5% Wooster spots.
(2) The fiber according to (1), wherein the thermoplastic matrix polymer is polyester.
(3) The fiber according to claim 1 or 2, wherein the elastic modulus is 110 to 1000 cN / dtex.
(4) The fiber according to (1) or (2), wherein the elastic modulus is 50 cN / dtex or more and less than 110 cN / dtex.
(5) The fiber according to any one of (1) to (4), containing 0.01 to 1 wt% of a transesterification inhibitor with respect to the whole polymer blend obtained by blending a dendritic polyester with a matrix polymer.
(6) The fiber according to any one of (1) to (3) and (5), wherein the fiber is a monofilament.
(7) A blended yarn in which the fiber according to any one of claims (1) to (2) and (4) is used as a core yarn.
(8) A fiber product using the fiber according to any one of (1) to (7) as at least a part thereof.

  With the fiber of the present invention, the yarn unevenness is small, and the elastic modulus per birefringence of the fiber can be improved. That is, if the birefringence is the same, the high elastic modulus can be reduced, and if the same elastic modulus is the low birefringence, the wear resistance can be improved by reducing the molecular orientation while maintaining the high elastic modulus. In combination with small thread spots, it can be suitably used particularly for screen wrinkles. Further, by using it as a component of a spun fiber, it is possible to obtain a fiber that can easily form a core yarn even in a low molecular orientation, and it is possible to provide a fiber that is optimal for high-grade clothing.

  The dendritic polyester referred to in the present invention is a kind of hyperbranched polymer, but the dendritic polyester used in the present invention is composed of aromatic oxycarbonyl units (P), aromatic and aliphatic dioxy units (Q), and It contains a structural unit composed of an aromatic dicarbonyl unit (R) and a trifunctional or higher functional organic residue (B). The dendritic polyester used in the present invention comprises a structural unit comprising an aromatic oxycarbonyl unit (P), an aromatic and aliphatic dioxy unit (Q), and an aromatic dicarbonyl unit (R) and a trifunctional or higher functional organic residue. It is a dendritic polyester containing a group (B) and having a B content in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester.

  Here, the aromatic oxycarbonyl unit (P), the aromatic and aliphatic dioxy unit (Q), and the aromatic dicarbonyl unit (R) are structural units represented by the following formula (1), respectively. Is preferred.

  Here, R1 and R3 are each an aromatic residue, and R2 is a residue containing both aromatic and aliphatic. R1, R2, and R3 may each include a plurality of structural units.

  Examples of the aromatic residue include a substituted or unsubstituted phenylene group, naphthylene group, and biphenylene group. Examples of the aliphatic residue include ethylene, propylene, and butylene. R1, R2 and R3 are preferably at least one structural unit selected from structural units represented by the following formulae, and R2 is an aromatic residue (R2-1) and an aliphatic residue. (R2-2) are both included.

  However, in formula, n is an integer of 2-8.

  In the dendritic polyester of the present invention, the trifunctional or higher functional organic residue (B) is selected directly from an ester bond and / or an amide bond, or selected from P, Q and R constituting the branch structure part (D). The basic skeleton is a branched structure of three or more branches connected through a structural unit. The branched structure may be formed of a single basic skeleton such as three branches and four branches, or a plurality of basic skeletons such as three branches and four branches may coexist. It is not necessary for all of the polymers to be composed of the basic skeleton, and other structures may be included at the ends, for example, for end-capping. When B is a trifunctional organic residue, the dendritic polyester has a structure in which all three functional groups of B have reacted, a structure in which only two have reacted, and 1 A structure that reacts with only one may be mixed. Preferably, the structure in which all three functional groups of B have reacted is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more based on the entire B. When B is a tetrafunctional organic residue, the dendritic polyester has a structure in which all four functional groups of B are reacted, a structure in which only three are reacted, two A structure in which only one reacts and a structure in which only one reacts may be mixed. Preferably, the structure in which all four functional groups of B are reacted is preferably 10 mol% or more with respect to the entire B, and the structure in which three functional groups are reacted is preferably 20 mol% or more, more preferably four functional groups. The structure in which the functional group is reacted is 20 mol% or more with respect to the entire B and the structure in which three functional groups are reacted is 30 mol% or more with respect to the entire B, more preferably the structure in which four functional groups are reacted is the entire B The structure in which three functional groups react with each other at 25 mol% or more is 35 mol% or more with respect to the entire B.

  B is preferably an organic residue of a trifunctional compound and / or a tetrafunctional compound, and most preferably an organic residue of a trifunctional compound.

  The above three-branch basic skeleton is schematically represented by the formula (2). Further, the above four-branch basic skeleton is schematically represented by the formula (3).

  The dendritic polyester of the present invention preferably exhibits molten liquid crystallinity. The term “showing melt liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature (25 ° C.). The liquid crystal state is a state showing optical anisotropy under shear.

  In order to exhibit molten liquid crystallinity, the basic skeleton in the case of three branches is a branched structure portion (D) in which B is composed of a structural unit selected from P, Q and R as shown by the following formula (4): It is preferable that it couple | bonds through.

  Similarly, the basic skeleton in the case of four branches is preferably a structure represented by the following formula (5).

  The trifunctional organic residue B is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example, aliphatic compounds such as glycerol, 1,2,3-tricarboxypropane, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, α Residues of aromatic compounds such as resorcinic acid, β-resorcinic acid, γ-resorcinic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid, melamine are preferred Used. A residue of an aromatic compound represented by the following formula is more preferable.

  Specific examples of the above trifunctional organic residues include residues such as phloroglucinol, trimesic acid, trimellitic acid, trimellitic anhydride, α-resorcylic acid, 4-hydroxy-1,2-benzenedicarboxylic acid Are preferred, more preferred are residues of trimesic acid and α-resorcylic acid, and most preferred are residues of trimesic acid.

  The tetrafunctional or higher functional organic residue B is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example, erythritol, pentaerythritol, threitol, xylitol, glucitol, mannitol, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetraol, 1,2,3,4,5- Cyclohexanepentaneol, 1,2,3,4,5,6-cyclohexanehexaneol, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5-cyclohexanepentacarboxylic acid, 1, Residues of aliphatic compounds such as 2,3,4,5,6-cyclohexanehexacarboxylic acid, citric acid, tartaric acid, 1,2,4,5-benzenetetraol, 1,2,3,4- Benzenetetraol, 1,2,3,5-benzenetetraol, 1,2,3,4,5-benzenepentaneol, 1,2,3,4,5, -Benzenehexaneol, 2,2 ', 3,3'-tetrahydroxybiphenyl, 2,2', 4,4'-tetrahydroxybiphenyl, 3,3 ', 4,4'-tetrahydroxybiphenyl, 3, , 3 ′, 5,5′-tetrahydroxybiphenyl, 2,3,6,7-naphthalenetetraol, 1,4,5,8-naphthalenetetraol, pyromellitic acid, merophanic acid, planitic acid, meritic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,2 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 5,5′-biphenyltetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthaleneteto All, 1,4,5,8-naphthalenetetraol, 1,2,4,5,6,8-naphthalenehexaol, 1,2,4,5,6,8-naphthalenehexacarboxylic acid, gallic acid, A residue of an aromatic compound such as A residue of an aromatic compound represented by the following formula is more preferable.

  Specific examples of the tetrafunctional organic residue of the above formula include 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5. -Residues such as benzenetetraol, pyromellitic acid, merophanic acid, planitic acid and gallic acid are preferred, and residues of gallic acid are particularly preferred.

  Further, the aromatic oxycarbonyl unit (P), aromatic dioxy unit (Q), and aromatic dicarbonyl unit (R) of the dendritic polyester are units constituting the branch structure portion (D) between the branches of the dendritic polyester. It is. p, q and r are the average contents (molar ratio) of the structural units P, Q and R, respectively, and preferably in the range of p + q + r = 1 to 10 moles with respect to 1 mole of the content b of B. . p + q + r is more preferably in the range of 2 to 6 moles. If the branch structure length is too long, an effect such as shear responsiveness based on a rigid and detailed dendritic structure and an effect of suppressing entanglement with the matrix polymer molecular chain are not preferable.

  The values of p, q and r are determined by, for example, dissolving dendritic polyester in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of deuterated chloroform, and performing nuclear magnetic resonance spectrum analysis of proton nuclei at 40 ° C. It can obtain | require from the peak intensity ratio derived from a structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. The average chain length of the branch structure portion (D) is calculated from the area intensity ratio with the peak corresponding to the content b of B, and is set as p + q + r. In this case, the three decimal places are rounded off.

  The ratio of p to q and the ratio of p to r (p / q, p / r) are preferably in the range of 5/95 to 95/5, more preferably 10/90 to 90/10, It is preferably 20/80 to 80/20. If it is this range, liquid crystallinity is easy to express and it is preferable. It is preferable to set the ratio of p / q and p / r to 95/5 or less because the melting point of the dendritic polyester can be within an appropriate range. Further, it is preferable that p / q and p / r be 5/95 or more because the melted liquid crystallinity of the dendritic polyester can be expressed.

  q and r are preferably substantially equimolar, but either component can be added in excess to control the end groups. The ratio of q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure. Here, the term “end structure” means the end of the branch structure portion (D). When the end is blocked, it means the end of the branch structure portion (D) closest to the end.

  In the formula (1), R1 is a structural unit derived from an aromatic oxycarbonyl unit, and specific examples thereof include a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. A structural unit derived from p-hydroxybenzoic acid is preferred, and a structural unit derived from 6-hydroxy-2-naphthoic acid can be used in combination. Further, structural units derived from aliphatic hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, and hydroxycaproic acid may be contained within a range not impairing the effects of the present invention.

  R2 is a structural unit containing both aromatic and aliphatic structures. Examples of the aromatic unit include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4. , 4'-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'- Examples include structural units derived from dihydroxydiphenyl ether, and aliphatic units include structural units derived from aliphatic diols such as ethylene glycol, propylene glycol, and 1,4-butanediol. A structural unit derived from 4,4'-dihydroxybiphenyl or ethylene glycol is preferred, and a structural unit derived from 4,4'-dihydroxybiphenyl and ethylene glycol is preferred from the viewpoint of controlling liquid crystallinity.

  In the dendritic polyester used in the present invention, it is particularly important that the R2 unit is a structural unit containing both aromatic and aliphatic. First, by adding aromaticity, the branch structure is given rigidity (preferably giving liquid crystallinity), entanglement with the matrix polymer molecular chain is suppressed, and elongation deformation is inhibited even in the case of large deformation such as spinning. This can be suppressed. Thereby, industrially sufficient spinnability (spinning property, stability, etc.) can be obtained, and the yarn unevenness can be greatly improved. In addition, it is possible to improve the elastic modulus per birefringence of the fiber by adding an appropriate amount of entanglement within a range that does not greatly inhibit the elongation deformation of the matrix polymer. Because it can. In the present invention, the entanglement of the molecular chain is controlled by mixing the aromatic and the aliphatic as described above, and the conventional anti-twisting effect of improving the spinnability and the unevenness of the yarn and the elastic modulus per birefringence is achieved at the same time. It is. Here, if the elastic modulus per birefringence is improved, if the birefringence is the same, the high elastic modulus can be achieved, and if the elastic modulus is the same, the low birefringence can be achieved. It is also possible to achieve both the elastic modulus and abrasion resistance of the fiber, which has been a trade-off in the past. For this reason, combined with industrial materials and small thread spots, it can be suitably used especially for screen wrinkles.

  R3 is a structural unit derived from an aromatic dicarbonyl unit such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4. , 4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid. A structural unit derived from terephthalic acid or isophthalic acid is preferred, and when both are used in combination, the melting point can be easily adjusted. In addition, a part of structural units derived from aliphatic dicarboxylic acids such as sebacic acid and adipic acid may be included within a range that does not affect the effects of the present invention.

  The branch structure portion (D) of the dendritic polyester of the present invention is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the properties are not greatly affected. It is. Among them, it is preferable to introduce an amide structure. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted, which is preferable. As a method for introducing an amide bond, p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, tetramethylenediamine pentamethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xyl Range amine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-Aminocyclohexyl Aliphatic, alicyclic or aromatic such as methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine It is preferable to copolymerize such an amine compound. Of these, copolymerization of p-aminophenol or p-aminobenzoic acid is preferred.

  Specific examples of the branch structure part (D) of the dendritic polyester include a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from ethylene glycol, and a structural unit derived from terephthalic acid, derived from p-hydroxybenzoic acid. Examples thereof include a structural unit, a structural unit derived from ethylene glycol, a structural unit derived from 4,4′-dihydroxybiphenyl, and a structural unit derived from terephthalic acid.

  Particularly preferred is that the branch structure part (D) is composed of the following structural units (I), (II), (III) and (IV). Here, (I) is a particularly preferred embodiment of the structural unit (P), (II) and (III) are the structural unit (Q), and (IV) is the structural unit (R).

  When the branch structural part (D) is composed of the structural units (I), (II), (III) and (IV), the content p of the structural unit (I) is based on p + q + r 30-90 mol% is preferable and 40-80 mol% is more preferable. Moreover, 70-5 mol% is preferable with respect to the total content q of (II) and (III), and, as for content q (III) of structural unit (VI), 60-8 mol% is more preferable. As described above, the content r of the structural unit (IV) is preferably substantially equimolar to the total content q of the structural units (II) and (III). May be added.

  The terminal of the dendritic polyester of the present invention is preferably a carboxyl group, a hydroxyl group, an amino group, or a derivative thereof. Examples of the hydroxyl derivative or carboxylic acid derivative include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester. It is also possible to end-block using a monofunctional epoxy compound, an oxazoline compound, an ortho ester, an acid anhydride compound, or the like. The end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method etc. are mentioned.

  Specifically, when blocking the hydroxyl terminal or acetoxy terminal, benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4- It is possible by adding methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid, and the like.

  Moreover, the carboxyl group terminal blockade can be performed by reacting a carboxylic acid-reactive monofunctional compound. Here, the carboxylic acid-reactive monofunctional compound refers to a compound having one functional group in the molecule that can react with carboxylic acid at room temperature or when heated to form an ester, amide, urethane, or urea bond. The carboxylic acid-reactive monofunctional compound reacts with the carboxylic acid group present at the molecular end of the dendritic polyester, and the monofunctional compound is introduced at the molecular end, thereby improving the residence stability and hydrolysis resistance of the dendritic polyester. When improved and further kneaded with another thermoplastic polymer, the degradation of the thermoplastic polymer can be suppressed, and the dispersibility of the dendritic polyester is improved, so that improvement in fluidity and physical properties can be expected.

  The carboxylic acid-reactive monofunctional compound that can be used in the dendritic polyester of the present invention is at least one compound selected from oxazoline, epoxide, orthoester, isocyanate, carbodiimide, and diazo compound. From the viewpoint of reactivity with carboxylic acid and handling properties, oxazoline, epoxide, orthoester, and isocyanate can be preferably used. The carboxylic acid-reactive monofunctional compound may be used alone or in combination of two or more carboxylic acid-reactive monofunctional compounds.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, and 2-butoxy. 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2 -Cyclopentyloxy-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline, 2-p-phenylphenoxy- -Oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2 -Sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline , 2-crotyl-2-oxazoline, 2-phenyl-2- Kisazorin, 2-biphenyl-2-oxazoline. Of these, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2 from the viewpoints of reactivity and affinity with dendritic polyester and heat resistance -Oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2-sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-biphenyl 2-Oxazoline is preferable, and 2-phenyl-2-oxazoline is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the epoxy compound include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N- Glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N- Glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidylmaleimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, o-phenylphenyl Sidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 3- (2-xenyloxy) -1,2-epoxypropane, allyl glycidyl ether, butyl glycidyl ether, lauryl glycidyl ether, benzyl glycidyl ether, cyclohexyl glycidyl ether, α -Cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate ether, ethylene oxide, propylene oxide, styrene oxide, octane oxide, glycidyl acetate, glycidyl propionate, glycidyl butanoate, pentanoic acid Glycidyl ester, hexanoic acid glycidyl ester, octanoic acid glycidyl ester, decanoic acid glycidyl And glycidyl ester of neodecanoic acid and glycidyl benzoate. Of these, ethylene oxide, propylene oxide, butyl glycidyl ether, phenyl glycidyl ether, and benzoic acid glycidyl ester are preferred, and benzoic acid glycidyl ester is particularly preferred from the viewpoints of reactivity and affinity with the dendritic polyester.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, ortho ester compounds include, for example, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, ortho Triethyl formate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tribenzyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate Triethyl, tripropyl orthobenzoate, tributyl orthobenzoate, tribenzyl orthobenzoate and the like can be mentioned. Of these, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate are preferred, and trimethyl orthoacetate or triethyl orthoacetate is particularly preferred from the viewpoints of reactivity and affinity with dendritic polyester and handling properties. .

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the isocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, Examples include decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, stearoyl isocyanate, and p-toluosulfonyl isocyanate. Of these, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and phenyl isocyanate are preferable from the viewpoint of reactivity and affinity with the dendritic polyester, and phenyl isocyanate is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the diazo compound include diazomethane, diazoethane, diazopropane, diazobutane, and trimethylsilyldiazomethane. Of these, diazomethane and trimethylsilyldiazomethane are preferably used from the viewpoint of reactivity and affinity with the dendritic polyester.

  Theoretically, it is possible to block the end by adding the organic compound used for blocking the end in an amount corresponding to the end group to be blocked. It is preferable to use 1.005 times equivalent or more, more preferably 1.008 times equivalent or more of the organic compound used for terminal blocking with respect to the equivalent amount of the terminal group to be blocked. Moreover, it is preferable that the addition amount of the organic compound used for terminal blockage is 2.5 times equivalent or less. If the amount of the compound used for terminal blocking is too small, the terminal blocking is not sufficient. On the other hand, if the addition amount is too large, an excessively added compound remains in the system and generates gas, which is not preferable.

  The content of B is determined from the viewpoint that the chain length of the branch structure portion (D) is a length suitable for the dendritic polyester to take a dendritic form, but a sufficient dendritic shape is formed. Therefore, it is important that the content of all monomers constituting the dendritic polyester is 7.5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. is there. On the other hand, in order to prevent the branch structure portion from being excessively crowded, the upper limit of the B content is important to be 50 mol% or less, preferably 45 mol% or less, preferably 40 mol% % Or less is more preferable.

  The dendritic polyester of the present invention may have a partially crosslinked structure as long as the properties are not affected.

  In the present invention, a method for producing a dendritic polyester can be produced according to a known polyester polycondensation method. A monomer containing at least one structural unit selected from the structural unit represented by R1, a monomer containing at least one structural unit selected from the structural unit represented by R2, and R3 A method of reacting a monomer containing at least one structural unit selected from structural units, and a trifunctional or higher polyfunctional monomer that forms a trifunctional or higher functional residue (B), A method is preferred in which the addition amount (mol) of the polyfunctional monomer is 7.5 mol% or more with respect to the total monomer (mol) constituting the dendritic polyester. The addition amount of the polyfunctional monomer is more preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more. Moreover, as an upper limit of addition amount, 50 mol% or less is preferable, More preferably, it is 33 mol% or less, More preferably, it is 25 mol% or less.

  Further, in the above reaction, after acylating a monomer containing at least one structural unit selected from structural units represented by R1, R2 and R3, a polyfunctional monomer having three or more functionalities is reacted. Is also preferable. Also, a mode in which a monomer containing at least one structural unit selected from the structural units represented by R1, R2 and R3, and a trifunctional or higher polyfunctional monomer is acylated and then subjected to a polymerization reaction is also available. preferable.

A preferred production method will be described by taking as an example the production of a dendritic polyester composed of the structural units (I), (II), (III) and (IV) and a trimesic acid residue.
(1) After synthesizing a liquid crystalline polyester oligomer by deacetic acid condensation polymerization from p-acetoxybenzoic acid, 4,4′-diacetoxybiphenyl, terephthalic acid and polyethylene terephthalate polymer, trimesic acid is added to cause deacetic acid polymerization reaction. Manufacturing method.
(2) A method for producing from p-acetoxybenzoic acid, 4,4′-diacetoxybiphenyl, terephthalic acid, polyethylene terephthalate polymer and trimesic acid by a deacetic acid condensation polymerization reaction.
(3) Liquid crystalline polyester oligomer by reacting p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid and polyethylene terephthalate polymer with acetic anhydride to acylate the phenolic hydroxyl group and then deaceticating polycondensation reaction , And further by adding trimesic acid and performing a deacetic acid polymerization reaction.
(4) p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, terephthalic acid, polyethylene terephthalate polymer and trimesic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then produced by deacetic acid polycondensation reaction how to.
(5) After synthesizing a liquid crystalline polyester oligomer from the phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid diphenyl ester and polyethylene terephthalate polymer by dephenol polycondensation reaction, trimesic acid is added to remove it. A method of producing by a phenol polycondensation reaction.
(6) A method for producing by dephenol polycondensation reaction from phenyl ester of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, terephthalic acid diphenyl ester, polyethylene terephthalate polymer and trimesic acid phenyl ester.
(7) Diphenyl carbonate is reacted with p-hydroxybenzoic acid, terephthalic acid, and trimesic acid to form phenyl esters, respectively, and 4,4'-dihydroxybiphenyl and polyethylene terephthalate polymer are added to produce by dephenol polycondensation reaction. how to.

  Of these, the production methods (1) to (4) are preferred, and the methods (3) and (4) are more preferred.

  In the production methods of (3) and (4), the amount of acetic anhydride used is preferably 0.95 equivalents or more and 1.10 equivalents or less of the total phenolic hydroxyl group from the viewpoint of chain length control. It is more preferable that it is not less than 1.08 equivalent and most preferably not less than 1.02 equivalent and not more than 1.05 equivalent. It is possible to control the terminal group by controlling the amount of acetic anhydride or adding an excess of either a dihydroxy monomer or a dicarboxylic acid monomer.

  In order to increase the molecular weight, an amount corresponding to the amount of carboxylic acid of trimesic acid is added in excess of dihydroxy monomer such as 4,4′-dihydroxybiphenyl to the dicarboxylic acid monomer, It is preferable to match the hydroxyl equivalent. On the other hand, when the carboxylic acid is intentionally left in the terminal group, it is preferable not to add the dihydroxy monomer as described above excessively. Furthermore, when the hydroxyl group is intentionally left at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid, and the amount of acetic anhydride used is less than 1.00 equivalent of the phenolic hydroxyl group. preferable.

  By these methods, the dendritic polyester of the present invention can be selectively provided with an end group structure rich in reactivity with various thermoplastic polymers. However, depending on the thermoplastic polymer used as the matrix polymer, it may be easier to control the dispersion state by blocking the ends with a monofunctional epoxy compound or the like in order to suppress excessive reactivity.

  When the deacetic acid polycondensation reaction is performed, a melt polymerization method in which the reaction is carried out at a temperature at which the dendritic polyester melts, optionally under reduced pressure, to distill a predetermined amount of acetic acid and to complete the polycondensation reaction, is preferable. For example, a predetermined amount of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, terephthalic acid, polyethylene terephthalate polymer and acetic anhydride are placed in a reaction vessel equipped with a stirring blade and a distillation pipe and provided with a discharge port at the bottom. Prepare. The mixture is heated with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, and then heated to 200 to 350 ° C. to perform a deacetic acid polycondensation reaction to distill acetic acid. When acetic acid is distilled to 50% of the theoretical distillation amount, a predetermined amount of trimesic acid is added and acetic acid is further distilled to 91% of the theoretical distillation amount to complete the reaction.

  As conditions for acetylation, the reaction temperature is preferably in the range of 130 to 170 ° C, more preferably in the range of 135 to 155 ° C. The reaction time is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.

  The polycondensation temperature is a temperature at which the dendritic polyester is melted, and is preferably a melting point of the dendritic polyester + 10 ° C. or higher. Specifically, for example, it is in the range of 200 to 350 ° C, and preferably 240 to 280 ° C. The atmosphere for polycondensation is satisfactory even under atmospheric pressure nitrogen, but a reduced pressure is preferable because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is preferably 0.1 mmHg (13.3 Pa) to 200 mmHg (26600 Pa), more preferably 10 mmHg (1330 Pa) to 100 mmHg (13300 Pa). Note that acetylation and polycondensation may be carried out continuously in the same reaction vessel, or acetylation and polycondensation may be carried out in different reaction vessels.

After the polycondensation reaction is completed, the reaction vessel is kept at a temperature at which the dendritic polyester melts, and is pressurized to, for example, 0.01 to 1.0 kg / cm ² (0.001 to 0.1 MPa), and the bottom of the reaction vessel The dendritic polyester is discharged in a strand form from the discharge port provided in. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets. The discharged dendritic polyester is cooled by passing through air or water, and then cut or pulverized as necessary.

  The obtained pellet-like, granular or powdery dendritic polyester further removes water, acetic acid and the like by heat drying or vacuum drying, if necessary. Further, in order to finely adjust the degree of polymerization, or to further increase the degree of polymerization, solid phase polymerization can also be performed. In the solid phase polymerization, for example, the dendritic polyester obtained as described above is subjected to a temperature range of a melting point of the dendritic polyester from −50 ° C. to a melting point of −5 ° C. (for example, 200 to 300 ° C.) under a nitrogen stream or under reduced pressure. And heating for 1 to 50 hours.

  The polycondensation reaction of the dendritic 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 dendritic polyester of the present invention preferably has a number average molecular weight of 1,000 to 40,000, more preferably 1,000 to 20,000, still more preferably 1,000 to 10,000, Preferably it is the range of 1,000-5,000. The number average molecular weight is a value measured as an absolute molecular weight by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the dendritic polyester is soluble.

  The melt viscosity of the dendritic polyester in the present invention is preferably 0.01 to 30 Pa · s, more preferably 0.5 to 20 Pa · s, and particularly preferably 1 to 10 Pa · s. In addition, this melt viscosity is a value measured by a Koka flow tester under the condition of a shear rate of 100 / s under the condition of the liquid crystal starting temperature of the dendritic polyester + 10 ° C.

In the present invention, by blending the above-mentioned dendritic polyester with a matrix polymer, an effect of improving fluidity can be obtained and the spinning temperature can be lowered. This mechanism is estimated as follows. That is, J. et al. Polym. Sci. Part B: Polum. Phys. , Vol. 34, 2433 (1996). According to the description, the viscosity of the polymer in the incompatible polymer blend is described by the molecular weight term + dispersion interaction term + slip effect term, but the dendritic polyester used in the present invention has a low molecular weight and dispersion interaction for the molecular weight term. It is considered that the fluidity of the polymer blend is improved by the dendritic structure for the term and the liquid crystal effect for the slip effect term. That is, it is possible to obtain a higher fluidity improving effect that cannot be obtained by simply blending a low-viscosity polymer, a liquid crystal polymer, or an aliphatic hyperbranched polymer. Also, Macromolecule, vol. 38, 10571 (2005). Then, when the sizes of the hyperbranched polymer and the normal linear polymer were compared with the same molecular weight, the hyperbranched polymer had a molecular size of 1/5 or less. Furthermore, Polymer, vol. According to 45,7491 (2004), where the entanglement between molecules in hyperbranched polymers and conventional linear polymer was evaluated in the second virial coefficient A _2, the hyperbranched polymer A ₂ is 2 orders of magnitude smaller, self molecules It has been reported that there is very little intermolecular entanglement. From the above, it is considered that the dendritic polyester used in the present invention behaves like an organic nanoparticle in the matrix polymer and improves the fluidity. Furthermore, as described above, the R2 portion is a mixture of aromatic and aliphatic, thereby controlling the entanglement of the molecular chain, and the conventional anti-twisting effect of improving spinnability, yarn spot and elastic modulus per birefringence. They are both compatible.

  In the present invention, it is important to blend the above-described dendritic polyester into a matrix polymer composed of 0.1 to 10 wt% of a thermoplastic polymer.

  Examples of the matrix polymer include polyester, polyamide, polyphenylene sulfide, polyolefin, polycarbonate, polyester carbonate, polyimide, polyamideimide, polyether ketone, polyether ether ketone, and polyvinylidene fluoride. Among them, polyester having high versatility and relatively high elastic modulus and polyphenylene sulfide having excellent heat resistance and chemical properties are preferable. In particular, a high molecular weight polyester having an intrinsic viscosity of 1.0 dL / g or more has an extremely high melting point, although its melting point is not so high. Therefore, the spinning temperature may be increased by about 10 to 20 ° C. compared to the case of polyester for clothing. This is useful from the viewpoint of maintaining a high molecular weight by inhibiting decomposition and thermal decomposition. In addition, although not general-purpose, such as polyether ketone, polyether ether ketone, polyimide, polyvinylidene fluoride, and the like, the polymer species whose spinning temperature is usually quite high, from the effect of lowering the spinning temperature due to the fluidity improvement effect, Preferred polymer. In particular, the effect of lowering the spinning temperature is useful for polymers that easily generate corrosive substances and harmful substances such as polyvinylidene fluoride. In the case of a high molecular weight polymer having a molecular weight of 100,000 or more, the effect of suppressing the entanglement of molecular chains is useful. In particular, in the case of a polymer having a high molecular weight but a low thermal decomposition temperature, such as polylactic acid, if the spinning temperature can be lowered, not only the molecular weight decrease due to hydrolysis or thermal decomposition can be suppressed, but also the decomposition gas It is very useful because it can suppress the occurrence of In the present invention, from the viewpoint of versatility, it is preferable to use a high molecular weight polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) having an intrinsic viscosity of 1.0 dL / g or more as the matrix polymer. It is also highly useful to use a polylactic acid having a weight average molecular weight of 150,000 or more, or a stereocomplex polylactic acid having an improved melting point, as the matrix polymer, which has a high spinning temperature and is easily pyrolyzed.

  In another aspect, when polyspinning polylactic acid and PET, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), nylon 6, nylon 66, or the like, the polymer used as a partner for polylactic acid is used as a polymer. The addition of dendritic polyester is also useful because it can lower the spinning temperature of composite spinning by improving fluidity.

  In another aspect, the ability to lower the spinning temperature also reduces the temperature in the vicinity of the spinneret, thereby reducing the contamination of the die and improving the spinning stability over time, and extending the die correction cycle, resulting in production efficiency. Can be improved. In particular, when titanium oxide is contained in PBT or PTT, there is a problem that dirt having titanium oxide as a nucleus is likely to be deposited on the outer periphery of the mouthpiece hole as compared with the case of PET. It is also possible to contribute to the suppression.

  Moreover, if the blend rate of dendritic polyester is 0.1 wt% or more, the spinning temperature lowering effect and the elastic modulus improving effect by improving fluidity are recognized, and if it is 0.7 wt% or more, the effect is further improved and preferable. On the other hand, when the blend ratio is 10 wt% or less, good spinnability and yarn unevenness can be achieved without significantly inhibiting elongation deformation. Preferably it is 2 wt% or less.

  In the fiber of the present invention, it is important that the Wooster spot (U%), which is an index of thick and thin threads, is 5% or less. As a result, the unevenness in the longitudinal direction of the strength and elastic modulus of the yarn is reduced, and the material design is facilitated particularly when used for industrial materials. Further, from the viewpoint of clothing fibers, U% is preferably 2% or less, and more preferably 1.2% or less, in order to suppress stained spots. Although U% is preferably as small as possible, the practical lower limit is 0.1%. In order to improve the spinnability and reduce the yarn unevenness, it is useful to suppress the reaction between the dendritic polyester and the matrix polymer, and endblocking of the dendritic polyester is effective. In particular, the carboxy terminus is preferably blocked.

  Moreover, addition of a transesterification reaction inhibitor is also effective, and it is preferable to add 0.01 to 1 wt% with respect to the whole polymer blend. Addition of a large amount is preferable for reaction suppression, but if added excessively, spinnability and yarn unevenness may be lowered, so 0.05 to 0.2 wt% addition is more preferable.

  The transesterification inhibitor used in the present invention suppresses the reaction between the dendritic polyester and the matrix polymer, and is particularly effective when the matrix polymer is polyester and / or polyamide. This has a function of coordinating as a monodentate ligand or a polydentate ligand with respect to residual metal ions and the like and deactivating the catalytic ability of metal ions. Examples thereof include triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, phosphorus compounds, sulfur compounds, and the like. Specific examples are given below.

  Specific examples of the triazole compound include benzotriazole, 3- (N-salicyloyl) amino-1,2,4-triazole, and the like.

  Specific examples of the polyvalent amine include 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5. .5] Undecane, ethylenediamine-tetraacetic acid, alkali metal salt (Li, Na, K) of ethylenediamine-tetraacetic acid, N, N′-disalicylidene-ethylenediamine, N, N′-disalicylidene-1, 2 -Propylenediamine, N, N ''-disalicylidene-N'-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole and the like.

  Specific examples of the hydrazine derivative-based compound include decamethylene dicarboxyl acid-bis (N′-salicyloyl hydrazide), bis (2-phenoxypropionyl hydrazide) isophthalate, N-formyl-N′-salicyloyl hydrazine. 2,2-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide, nickel-bis (1-phenyl-3-methyl) -4-decanoyl-5-pyrazolate), 2-ethoxy-2′-ethyloxanilide, 5-t-butyl-2-ethoxy-2′-ethyloxanilide, N, N-diethyl-N ′, N '-Diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid -Bis (benzylidenehydrazide), thiodipropionic acid-bis (benzylidenehydrazide), isophthalic acid-bis (2-phenoxypropionylhydrazide), bis (salicyloylhydrazine), N-salicylidene-N'-sali Siloylhydrazone, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tetrakis [2-tert-butyl-4-thio (2′-methyl-) 4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-t-butyl- 4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5 Methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-5′-) t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-dicarboxylic acid-di-salicyloylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2′-methyl-) 4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-) Hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (H Rokishiechiru) oxamide - diphosphite, N, N'-bis [2- [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, and the like.

  Examples of phosphorus compounds include compounds containing a phosphorus atom in the molecule, such as phosphate compounds and phosphite compounds.

  Specific examples of the phosphate compound include aliphatic phosphate esters (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, dibutyl phosphate, monobutyl phosphate, di ( 2-ethylhexyl) phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, dicyclopentyl high positive phosphate, etc.), aromatic phosphates (triphenyl phosphate, tricresyl phosphate, trikis) Silenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate Phosphate, tris (p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, dipyrrocatechol high positive phosphate, etc. Aliphatic-aromatic phosphate ester (diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, ethyl pyrocatechol phosphate And the like, and the condensates thereof.

  Specific examples of the phosphite compound include tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-Methyl-4-ditridecylphosphite-5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphie , Tris (nonylphenyl) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.

  The sulfur compound may contain a sulfur atom in the molecule. Specifically, dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3 '-Thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4 , 8,10-tetraoxaspiro [5,5] undecane and the like.

  These transesterification reaction inhibitors tend to deactivate the catalytic ability of metal ions by selecting a substance that is strongly coordinated with residual metal ions contained in the polymer and easily forms a complex.

  In addition, since the polymer is blended and spun at a temperature higher than the melting point of the polymer, the heat resistance of the transesterification inhibitor itself is important. Among the transesterification reaction inhibitors of the present invention, compared to hydrazine derivative-based compounds and sulfur-based compounds, phosphorus-based compounds are preferable because they have high heat resistance and are not easily colored, and among these, aliphatic phosphate-based compounds are particularly preferable. .

  In the fiber of the present invention, the elastic modulus per birefringence can be made higher than when no dendritic polyester is added, which is estimated as follows. That is, as described above, by including not only aromatic but also aliphatic as a branch structure, it has a proper entanglement of molecular chains within a range that does not greatly inhibit the extension deformation of the matrix polymer, and locally. A part with a strong constraint of the molecular chain is induced, and this is further strengthened in the elongation deformation process. As a result, even if the overall elongation (stretching degree) is not so high (even if the birefringence is low), there is a part where the molecular chain is strongly constrained locally. Is thought to have a significant impact. From the standpoint of improving the elastic modulus, the higher the blend ratio of the above-mentioned dendritic polyester, the better. However, the upper limit is determined from the viewpoint of spinnability and yarn unevenness. Even with a high molecular weight PET having an intrinsic viscosity of 1.0 dL / g or more, a sufficient effect can be obtained by adding 1 wt%.

  In the fiber of the present invention, if the elastic modulus is 110 cN / dtex or more, it is suitable for industrial materials and is preferable. In this case, a higher elastic modulus is preferable, but a practical upper limit of the elastic modulus is 2000 cN / dtex. In addition, because of its relatively low birefringence, bending fatigue and wear characteristics are improved compared to conventional products. In addition to rubber reinforcement applications such as tire cords and tire cap layer materials, fishing nets and agricultural materials, screen rods, etc. Also, it can be suitably used. In particular, screen wrinkles are used for electrode printing of flat displays that are thinner and more accurate than conventional textile printing, and further demands for finer monofilaments and higher elastic modulus are required. It is coming. However, to achieve this, simply stretching the fiber at a high magnification has a problem that molecular orientation becomes too high (birefringence becomes too high), wear resistance is reduced, and fluffing during weaving frequently occurs. . However, in the present invention, even if the birefringence is low, the elastic modulus is high, so that such a problem can be solved. In particular, when used for a screen, it is preferable to use a monofilament. Further, when applied to a screen ridge, the elastic modulus is preferably 110 cN / dtex or more and the birefringence is 0.180 or less.

  Moreover, in the fiber of this invention, if an elasticity modulus is 50 cN / dtex or more and less than 110 cN / dtex, it can be used conveniently for the clothing use etc. It is particularly useful as a core yarn for blended yarn. Here, the mixed yarn is a mixture of two different types of fibers, and as a mixing method, spinning mixed fiber, air entanglement, intertwisting, composite false twist, or the like can be used. In particular, in the case of spun fibers, it is difficult to adjust the molecular orientation because the spinning is usually carried out from the same die and the take-up speed is almost the same. For example, when spinning and blending thin and fine single yarn fines, the thick fine yarn is used as the core yarn and positioned in the relatively inner layer portion of the mixed yarn, and the fine yarn is used as the sheath yarn and the relatively outer layer portion. However, in reality, the fine-definition yarn has a higher molecular orientation (higher birefringence), so the fine-definition yarn forms the core yarn, contrary to expectations, due to the tension balance during stretching. It was normal. However, blending the above-mentioned dendritic polyester on the side of the thick yarn makes it easier to form a core yarn because the elastic modulus is high even if the birefringence of the yarn is low, and it is possible to arrange the yarn as expected. It becomes.

  In the fiber of the present invention, the strength is preferably 2 cN / dtex or more, and the practical upper limit is 20 cN / dtex. Further, the elongation is preferably 2 to 60% for the drawn yarn, particularly 2 to 15% in the industrial material field where a high elastic modulus is required, and 25 to 60% for clothing. The cross-sectional shape of the fiber can be appropriately selected from a round cross-section, a multi-leaf cross-section such as a trilobe, a hollow shape, a star shape, and an irregular shape.

  The above-described fibers can be made into various fiber products such as fiber winding packages, tows, cut fibers, cotton, fiber balls, cords, piles, knitted fabrics, nonwoven fabrics, paper, and liquid dispersions.

  An example of a method for obtaining the fiber of the present invention will be described. The dendritic polyester is as described above, and for blending and fiberizing, for example, the following methods can be used. That is, a dendritic polyester having a molecular weight in the range of 2000 to 5000 having a terminal acetyl group blocked with benzoic acid in a dendritic polyester composed of the above structural units (I) to (IV) and a trimesic acid residue and a matrix polymer Is dried if necessary and introduced into a twin screw extruder. At this time, the blending apparatus is preferably a biaxial extrusion kneader in order to reduce blend spots. Here, the produced polymer blend may be guided directly to a spinning machine or may be once pelletized as a master pellet. In order to save labor, kneaded direct spinning is preferable, but master pelletization is preferable in order to provide versatility such as making several varieties having different dendritic polyester blend ratios and polyester molecular weights. Also, in the case of kneaded direct-spun yarns, unlike a single-screw extrusion kneader, in a biaxial extrusion kneader, foaming induced in the kneader is difficult to escape to the charging side, so that the foam is mixed into the fiber and the yarn Cutting may occur frequently. For this reason, in particular, when a high viscosity polymer such as high molecular weight polyester is used as the matrix polymer, it is preferable to perform an operation of venting on the discharge side of the biaxial extrusion kneader to remove bubbles. In addition, it is preferable to vent when a piece of gut frequently occurs in the case of master pelletization. Further, in the present invention, due to the good fluidization effect due to the addition of the dendritic polyester, the screw torque is reduced at the same temperature as compared with the case where it is not added, so that the kneading temperature can be lowered. As a result, thermal decomposition, thermal denaturation, hydrolysis and the like of the polymer can be suppressed, and the high molecular weight and easy processability inherent to the virgin polymer can be easily utilized.

  In the case of resin processing, mechanical properties (such as improved elastic modulus) and gas barrier properties are often improved by mixing a large amount of inorganic filler such as glass fiber, but in the case of fiberization, inorganic filler is mixed. In such a case, the filter in the spinning machine may be clogged and the filtration pressure may increase rapidly, or the spinneret hole may be clogged with inorganic fillers and spinning may become impossible. Even if spinning is not possible, the discharge of the polymer from the spinneret hole is not stable, and problems such as frequent thread breakage and deterioration of yarn unevenness may occur. For this reason, in the case of fiberization, unlike resin processing, it is better not to mix the inorganic filler, and even if mixed, it is less than 0.5 wt% with respect to the entire blend polymer. When the inorganic filler is mixed in an amount of 0.5 wt% or more, U% cannot be 5% or less. The term “inorganic filler” as used herein means that 80 wt% or more is composed of an inorganic substance, the average diameter in terms of circle is 10 nm or more, and the average length is 100 nm or more.

  When master pelletized with the above dendritic polyester blend, it is diluted with a virgin polymer in the spinning process, but at this time, it is preferable to use a biaxial extrusion kneader from the viewpoint of uniformity of bun-lend. This is because, in the present invention, the degree of good fluidization effect varies depending on the dendritic polyester blend ratio, so if the blend is not uniform in the polymer blend, screw torque, tip pressure, filtration pressure, back pressure of the base, and spinning stress This is because spots such as the above occur and stable spinning may become impossible. When a uniaxial extrusion kneader is unavoidably used, a kneading function such as dull mage is added, and a static kneader is provided near the discharge of the uniaxial extrusion kneader or in the spinning machine or spinning pack to sufficiently homogenize the blend. preferable.

  As described above, because of the good fluidization effect due to the dendritic polyester blend, the kneader temperature can be lowered compared to the case where it is not added, but the set temperature can also be lowered for the spinning machine, for example, Even when the spinning temperature must be significantly higher than the melting point due to the high viscosity due to the high molecular weight polymer, it can be lowered to 5 ° C. or more by addition of dendritic polyester. This effect is more pronounced with higher viscosity polymers. In addition, the good fluidization effect stabilizes the discharge of the polymer from the spinneret hole, and the yarn unevenness can be reduced even in high-viscosity polymer spinning in which spinning is inherently unstable and yarn unevenness is likely to occur.

  In addition, the dendritic polymer used in the present invention introduces an aromatic component into the branch structure to improve rigidity, preferably to exhibit liquid crystallinity, and since it is difficult to entangle with the matrix polymer molecular chain, the elongation deformation becomes smooth. This not only improves spinnability and reduces yarn unevenness, but also enables high-speed spinning, which was difficult with the addition of an aliphatic hyperbranched polymer. This is also an effect peculiar to the elongation deformation field called spinning. On the other hand, the dendritic polymer used in the present invention is mixed with an aliphatic component in the branch structure, so that there is moderate molecular chain entanglement and an improved elastic modulus per birefringence, but this effect is also high speed spinning and high magnification This effect is strongly manifested in an extreme extensional deformation field such as stretching.

  In the present invention, the spinning temperature is preferably lowered by 5 to 20 ° C. as compared with the case where no dendritic polyester is added. More preferably, it is a 7-15 degreeC fall. The spinning speed varies depending on the physical properties of the matrix polymer and the purpose of the fiber, but can be about 500 to 6000 m / min. In particular, when a high elastic modulus is required for industrial material applications, it is preferable to use a high molecular weight polymer, set to 500 to 1500 m / min, and then stretch at a high magnification.

  In stretching, it is particularly preferable to set the preheating temperature appropriately. This is because the dendritic polyester used in the present invention may have a softening temperature such as a glass transition temperature higher than 70 ° C. For example, at about 85 to 95 ° C, which is a normal preheating temperature of PET, the dendritic polyester is in the process of stretching. As a result of acting as a foreign object, the toughness of the drawn yarn may be reduced. This effect is particularly prominent as the film is stretched at a high magnification. For this reason, even if the addition amount of dendritic polyester is trace amount, it is preferable to set preheating temperature more than the glass transition temperature and softening temperature of dendritic polyester. The upper limit of the preheating temperature is preferably a temperature at which yarn path disturbance does not occur due to spontaneous elongation of the fiber during the preheating process. This preheating temperature setting at the time of drawing can also contribute to the reduction of yarn unevenness.

  In addition, in the high elastic modulus fineness monofilament used for the screen wrinkle, it is highly molecularly oriented to improve the elastic modulus, but this alone decreases the wear resistance, and fluffing may occur frequently during the weaving process, At this time, relaxation heat treatment may be performed to reduce molecular orientation and avoid this. However, since the elastic modulus also decreases at the same time, the elastic modulus and the wear resistance are contradictory in the prior art, but in the present invention, since the elastic modulus per birefringence is high, low orientation by relaxation heat treatment is not necessary, This contradiction can be solved. Also, because it is fine filament monofilament spinning, it has a low discharge rate, the polymer residence time in the spinning machine is long, and gelation is likely to occur due to thermal degradation of the polymer due to abnormal residence, which induces monofilament nodes There is a case. This section is an abnormally thick part of the fiber, which causes a weaving defect. For this reason, this section should be zero, but there was no good means other than the device of the spinning machine, the spinning pack and the base structure. However, in the present invention, since the kneader temperature and the spinning temperature, which are the melting part, can be lowered, the above problems can be alleviated even with a low discharge amount, and the occurrence of knots can be suppressed, so that the industrial value is high.

  Further, when the function-added component made of polyester or polyamide is spun simultaneously, the decomposition, modification and deterioration of the function-added component can be suppressed even if the function-added component has low heat resistance.

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

A. Absolute molecular weight The absolute molecular weight of dendritic polyester is GPC-MALLS (gel permeation chromatograph (Shodex GPC-101) -light scattering detector (DAWN HELEOS made by Wyatt) using a solvent in which dendritic polyester is soluble. )), The sample concentration was 0.04%, and the measurement temperature was 23 ° C.

B. Weight average molecular weight The weight average molecular weight of the thermoplastic matrix polymer of the present invention is a value in terms of standard PMMA measured by gel permeation chromatography (GPC). The GPC measurement was performed using a WATERS differential refractometer WATERS410 as a detector, a pump using MODEL510 high performance liquid chromatography, and a solvent using hexafluoroisopropanol.

  However, the weight average molecular weight of polylactic acid was determined as follows. THF (tetrohydrofuran) was mixed with the sample chloroform solution to obtain a measurement solution. This was measured at 25 degreeC using GPC WATERS2690 by WATERS, and the weight average molecular weight was calculated | required in polystyrene conversion.

C. Intrinsic Viscosity of Polyester The intrinsic viscosity of polyester was dissolved in o-chlorophenol and measured at 25 ° C. using an Ostwald viscometer.

D. Relative viscosity of nylon Nylon was dissolved in 98% sulfuric acid aqueous solution and adjusted to a concentration of 0.01 g / mL, and then measured at 25 ° C. using an Ostwald viscometer.

E. Chemical composition ratio of dendritic polyester The chemical composition ratio of dendritic polyester is dissolved in a mixed solvent of pentafluorophenol / deuterated chloroform (50/50) using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL). 1H-NMR measurement was performed at 40 ° C., and the chemical composition ratio of each component was calculated from the peak intensity ratio.

F. Melting point and glass transition point Using a DS Instruments 2SC Modulated DSC manufactured by TA Instruments, the peak top temperature indicating the melting of the polymer at 2nd run was taken as the melting point of the polymer. The temperature rising rate at this time was 16 ° C./min, and the sample amount was 10 mg.
Similarly, the midpoint of the region showing stepwise endotherm at 2nd run was taken as the glass transition point.

G. Liquid crystal starting temperature The temperature at which the entire field of view starts to flow as measured with a shear stress heating device (CSS-450) at a shear rate of 1.0 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times. It was.

H. Worcester spots on fibers (U%)
Measurement was performed in a normal mode at a yarn feeding speed of 200 m / min using a USTER TESTER 4 manufactured by Zerbegger Worcester.

I. Fiber mechanical properties (strength, elongation, elastic modulus)
At room temperature (25 ° C.), an initial sample length = 200 mm, a pulling speed = 200 mm / min, and a load-elongation curve was obtained under the conditions shown in JIS L1013. Next, the load value at break was divided by the initial fineness, which was used as the strength, and the elongation at break was divided by the initial sample length to obtain a strong elongation curve. Further, the elastic modulus was obtained from the slope of a linear approximation of the initial rising portion of the load-elongation curve.

J. et al. Birefringence of fiber The retardation and path length of a single yarn were measured with an OLIMPUS BH-2 polarizing microscope to determine birefringence.

K. Evaluation of wear resistance The wear resistance was evaluated according to Japanese Patent Application Laid-Open No. 2004-232182. A thread is applied to a 3 mm satin metal bar at a contact angle of 35 °, and the thread tension is 1.5 cN / dtex at a position of 340 mm from the metal bar. And a reciprocating motion with a stroke length of 30 mm and a speed of 100 times / min was given, and the number of reciprocations in which fluff (peeling and fibrillation) occurred was measured. The measurement was performed 5 times, and the average value was obtained.

Reference Example 1 (Synthesis of Dendritic Polyester A-1)
In a reaction vessel equipped with a stirring blade and a distillation tube, 48.0 g (0.35 mol) of p-hydroxybenzoic acid, 30.9 g (0.17 mol) of 4,4′-dihydroxybiphenyl, 5.41 g of terephthalic acid ( 0.033 mol), 10.4 g (0.054 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 42.0 g (0.20 mol) of trimesic acid, and 76.3 g of phenolic anhydride (phenolic hydroxyl group) A total of 1.1 equivalents) was charged, and the mixture was allowed to react at 145 ° C. for 1.5 hours with stirring under a nitrogen gas atmosphere. After the reactor internal temperature reached 250 ° C., 14.7 g (0.12 mol) of benzoic acid was added and the temperature was raised to 280 ° C. When 100% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (A-1).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (A-1) was found to have an R portion structure having a p-oxybenzoate unit content p of 2.0, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q is 0.5, the terephthalate unit content r is 0.5, and p + q + r = 3. The branching point, that is, the content of B is 25 with respect to the total monomers constituting the dendritic polyester. Mol%. The terminal structures were carboxylic acid and benzoic acid ester.

  The obtained dendritic polyester resin had a melting point Tm of 182 ° C., a liquid crystal starting temperature of 163 ° C., and an absolute molecular weight of 5500.

Reference Example 2 (Synthesis of dendritic polyester A-2)
In a reaction vessel equipped with a stirring blade and a distillation pipe, 66.30 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, 7.48 g of terephthalic acid ( 0.045 mol), 14.40 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 42.72 g (0.28 mol) of α-resorcylic acid and 78.26 g of acetic anhydride. (1.08 equivalent of the total phenolic hydroxyl groups) was charged and reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere. Thereafter, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled out, 25.6 g of benzoic acid (0.21 mol; 1.000 times the theoretical acetoxy terminal). ) Was added to distill the acetic acid to 100%, heating and stirring were stopped, and the contents were discharged into cold water to obtain a dendritic polyester resin (A-2).

  As a result of nuclear magnetic resonance spectrum analysis, this dendritic polyester resin (A-2) was found to have an R portion structure having a p-oxybenzoate unit content p of 1.32, 4,4′-dioxybiphenyl units and ethylene oxide. The unit content q was 0.33, the terephthalate unit content r was 0.33, p + q + r = 2, and the branching point content was 30 mol%. The terminal structure was carboxylic acid and acetyl group.

  The obtained dendritic polyester resin had a melting point Tm of 182 ° C., a liquid crystal starting temperature of 152 ° C., and an absolute molecular weight of 6500.

Reference Example 3 (Synthesis of Aliphatic Hyperbranched Polymer A-3)
An aliphatic hyperbranched polymer was synthesized according to JP 2005-513186 A.

Examples 1-5, Comparative Example 1
After the dendritic polyester (A-1) synthesized in Reference Example 1 and high molecular weight PET having an intrinsic viscosity of 1.11 dL / g (weight average molecular weight = 25,500) were dried, they were weighed separately and independently biaxial An extrusion kneader was charged. At this time, the amount of dendritic polyester added was 1 wt% with respect to the polymer blend. Venting was performed on the discharge side of the biaxial extrusion kneader to eliminate bubbles. The kneader and spinning temperature were set as shown in Table 1. After discharging with a metal nonwoven fabric with an absolute filtration diameter of 10 μm at a discharge rate of 42.3 g / min, spinning was performed from a die with a round hole of 24 holes (φ = 0.6 mm), and after passing through a cooling air zone of Uniflow, Refueled and wound up.

  First, the spinning speed was set to 500 m / min, and the fluidity improvement effect by adding dendritic polyester was confirmed. As is clear from the comparison between Examples 1 to 5 and Comparative Example 1, the addition of the dendritic polyester causes a significant decrease in the spin pack pressure, and the fluidity of the high molecular weight PET is improved. It was confirmed. Further, the relationship between the spinning temperature and the spinning pack pressure is plotted in FIG. 1, but when compared with the same spinning pack pressure, the addition of 1 wt% dendritic polyester (Examples 1 to 5) can expect a spinning temperature lowering effect of 8 ° C. I understood it. As a precaution, the weight average molecular weight of PET was measured in Example 2 (addition of 1% by weight of dendritic polyester, spinning temperature of 295 ° C.), which was 18,600, and no addition of dendritic polyester (Comparative Example 1) It was the same value, and neither hydrolysis nor thermal decomposition was promoted by addition of dendritic polyester. Most of the obtained fibers had yarn spots with a sufficiently small level of U% of 1% or less.

Example 6
Furthermore, after drying Adeka ADEKA STAB AX-71, which is an aliphatic phosphate ester transesterification inhibitor, 0.1 wt% was added to the blend polymer, and the same as in Example 4 (spinning temperature 291 ° C.). As a result, the spin pack pressure was further reduced significantly, which was very effective in improving fluidity (Table 1, FIG. 1).

Examples 7-9
Next, when the amount of addition of the dendritic polyester (A-1) was changed variously and spinning was performed in the same manner as in Example 3, a fluidity improvement effect corresponding to the amount of addition was obtained. Although U% was 1.41% in Example 9, it is at a level where there is no practical problem. In Examples 7 and 8, it was 1% or less and excellent U%.

Examples 10 and 11
Next, the spinning speed was changed and spinning was carried out in the same manner as in Example 3. However, the spinning performance was good even when the spinning speed was increased, and U% was 1% or less.

Examples 12-18, Comparative Examples 2-8
The undrawn yarns obtained in Examples 2, 4, 5, 6 and Comparative Example 1 were subjected to drawing / heat treatment experiments. At this time, a 3 hot roller type stretching machine is used as the stretching machine, and stretching and heat treatment are performed through the feed roller (non-heated), first hot roller, second hot roller, third hot roller, delivery roller (non-heated) and yarn. Went. The first hot roller temperature (preheating temperature) is 90 ° C., the second hot roller temperature is 140 ° C., the third hot roller temperature is 230 ° C., and the draw ratio between the first hot roller and the second hot roller is 3.85. The stretching ratio between the second hot roller and the third hot roller was changed. Table 2 shows the total draw ratio from the feed roller to the delivery roller.

  In any case, there was no problem in stretchability, yarn breakage, fluff and the like did not occur, and U% was 1% or less. Moreover, although the relationship between birefringence and an elastic modulus was plotted in FIG. 2, Examples 12-18 which added dendritic polyester had the elastic modulus in the same birefringence 10% or more compared with Comparative Examples 2-8 which were not added. It was expensive. In particular, the region where the birefringence is smaller than around 0.185 is highly effective.

Example 19
Since the heat flow start temperature of the dendritic polyester (A-1) is as high as 160 ° C., the second hot roller temperature was changed to the temperature or higher, and the stretchability and the physical properties of the stretched yarn were examined. As the undrawn yarn, the product obtained in Example 2 was used, the draw ratio was 5.6 times, and the drawing and heat treatment were performed in the same manner as in Example 12.

  First, when the second hot roller temperature was 140 ° C., the total draw ratio of 5.7 times could not be drawn due to yarn breakage, but when the second hot roller temperature was 165 ° C., there was no yarn breakage and good drawability. there were. In addition, as the properties of the drawn yarn obtained, the strength was 7.1 cN / dtex, the elongation was 7.5%, the elastic modulus was 125 cN / dtex, the birefringence was 0.186, and U% = 0.78%. As a result of being able to stretch at a high magnification, improvement in mechanical properties was recognized. In addition, thread spots were also improved.

Example 20
PET having an intrinsic viscosity of 0.63 dL / g and the dendritic polyester (A-1) synthesized in Reference Example 1 were dried and then individually reduced in weight, and charged and blended independently in a biaxial extrusion kneader. At this time, dendritic polyester was 1 wt% with respect to the whole polymer blend. The kneading machine temperature was 285 ° C., and the blend polymer was introduced into the composite spinning machine. On the other hand, PET having an intrinsic viscosity of 0.63 dL / g was melted at 290 ° C. with a uniaxial extrusion kneader and again led to the same composite spinning machine. Then, the spinning temperature was set to 287 ° C., and the polymer blend was wound at a spinning speed of 3000 m / min so that the single yarn fineness was 6 dtex (12 filaments) and the PET was single yarn fineness 2 dtex (72 filaments). Then, using a belt nip type false twister, the mixed unstretched yarn was false twisted according to a conventional method at a heater temperature of 190 ° C. and a draw ratio of 1.8 times. In the obtained false twisted yarn cross-section, the thick fine yarn made of polymer blend is located relatively inside the mixed yarn to form the core yarn, and the fine fine yarn made of PET is relatively outside of the mixed yarn. And formed a sheath thread. In the spinning process, only a thick yarn composed of a polymer blend was wound up and U% was measured. As a result, U% = 0.98% was obtained. Furthermore, false twisting similar to that described above was added thereto, and U% of the false twisted yarn was measured, but the yarn unevenness was still good at 1.00%. The elastic modulus of this yarn was 60 cN / dtex.

  Then, a real twist of 700 T / m was added to the false twisted yarn made of this mixed fiber, and S twist / Z twist was alternately arranged to produce a 2/2 twill fabric using warp and weft. Further, the woven fabric was scoured at 80 ° C. and then set at 170 ° C., then dyed by a conventional method, and finished at 170 ° C. The resulting woven fabric was bulky and soft, and had excellent texture with a firm waist. Moreover, there was no dyeing spot and it was excellent in aesthetics.

Comparative Example 9
Spinning and false twisting were performed in the same manner as in Example 20 without adding the dendritic polyester. As a result, the thick fine yarn formed the sheath yarn and the fine fine yarn formed the core yarn. When this mixed fiber was used for warp and weft, a woven fabric was prepared and finished set in the same manner as in Example 20, and the core yarn and sheath yarn were reversed. The texture was inferior.

Example 21
The undrawn mixed fiber obtained in Example 20 was drawn and heat-treated at a preheating temperature of 90 ° C., a draw ratio of 1.85 times, and a heat setting temperature of 130 ° C. In the obtained drawn yarn cross-section, a thick yarn composed of a polymer blend is located relatively inside the blended yarn to form a core yarn, and a fine yarn composed of PET is located relatively outside the blended yarn. A sheath sheath thread was formed. In the spinning process, only a thick yarn composed of a polymer blend was wound up and U% was measured. As a result, U% = 0.98% was obtained. Furthermore, as described above, drawing and heat treatment were added, and U% of the drawn yarn was measured, but the yarn unevenness was still good at 0.82%. The elastic modulus of this yarn was 85 cN / dtex.

  A circular knitting was prepared using this mixed yarn, and after scouring at 80 ° C., intermediate setting was performed at 170 ° C., followed by dyeing by a conventional method and finishing setting at 170 ° C. The obtained knitted fabric was bulky and soft, and was excellent in texture with moderate elasticity.

Example 22
After drying the dendritic polyester (A-1) synthesized in Reference Example 1, high molecular weight PET having an intrinsic viscosity of 1.11 dL / g, and Adeka AX-71 manufactured by Adeka Co., which is a transesterification inhibitor, weighed separately. Then, it was charged in a twin-screw extrusion kneader. At this time, the dendritic polyester and the transesterification inhibitor were dry blended and charged. The addition amount was 1 wt% for the dendritic polyester and 0.1 wt% for the transesterification reaction inhibitor with respect to the polymer blend. Further, venting was performed on the discharge side of the biaxial extrusion kneader to eliminate the bubbles. The kneading machine and the spinning temperature were set to 287 ° C., spinning was performed from a die with a four-hole round hole, and after passing through a uniflow cooling air zone, it was divided into monofilaments, and then oiled, each wound as a monofilament. Then, a stretching heat treatment was performed in the same manner as in Example 16 at a total stretching ratio of 4.72 times and a second hot roller temperature of 165 ° C. to obtain a monofilament having a single yarn fineness of 8 dtex. The obtained fiber had U% = 0.78%, elastic modulus = 111 cN / dtex, birefringence = 0.178, strength = 5.5 cN / dtex, and elongation = 16.5%.

  When this abrasion resistance was evaluated, the number of reciprocations until the occurrence of fluff was 1000 times or more, indicating good abrasion resistance. This is a monofilament having a sufficient elastic modulus and wear resistance, and is optimal for a thin screen and a high precision screen screen for IT.

Comparative Example 10
Spinning was carried out in the same manner as in Example 22 without adding the dendritic polyester and the transesterification inhibitor and setting the kneader temperature and spinning temperature to 300 ° C. The discharge amount was adjusted according to the drawn yarn fineness. The obtained monofilament was drawn and heat-treated in the same manner as in Example 22 at a total draw ratio of 5.70, to obtain an 8 dtex monofilament. Its elastic modulus was 111 cN / dtex and birefringence was 0.186. Subsequently, the abrasion resistance was measured in the same manner as in Example 22. However, the abrasion resistance was 500 times until the occurrence of fluff, and the abrasion resistance was low.

Example 23
When the dendritic polyester (A-2) synthesized in Reference Example 2 was used for spinning in the same manner as in Example 2, the spinning pack pressure was 5.4 Pa · s, and a good fluidization effect could be confirmed. Moreover, U% of the obtained undrawn yarn was 0.94%, which was a sufficiently small yarn unevenness.
This was stretched and heat-treated in the same manner as in Example 12 at a second hot roller temperature of 165 ° C. and a total draw ratio of 5.20 times, U% = 0.77%, elastic modulus = 110 cN / dtex, birefringence = 0. A fiber with 180, strength = 5.8 cN / dtex, and elongation = 18% was obtained. The elastic modulus per birefringence is slightly lower than when A-1 is used, but it is a sufficient effect as compared with the case where it is not added.

Comparative Example 11
Using the aliphatic hyperbranched polymer (A-3) synthesized in Reference Example 3, spinning was carried out in the same manner as in Example 11. As a result, the spinning pack pressure was 8.0 Pa · s, A-1 and A of the present invention. Compared with the case of using -2, the good fluidization effect was small. Further, the spinning property was not as good as in Example 11 because the spinning was not stable and the yarn breakage occurred frequently.

Example 24
Poly L-lactic acid (weight average molecular weight 190,000) having an optical purity of 99% was dried, blended and melt-spun in the same manner as in Example 6. At this time, the kneader temperature was 220 ° C., the spinning temperature was 230 ° C., the discharge rate was 30 g / min, a nozzle with a hole diameter of 0.30 mm and 18 holes was used, and the spinning speed was 5000 m / min. The spinning pack pressure at this time was 16 MPa. Since the spinning temperature could be lowered below the temperature at which polylactic acid was significantly decomposed (240 ° C.), generation of decomposition gas could be suppressed. U% of the obtained high speed spinning fiber was 0.81%.

Comparative Example 12
Melt spinning was carried out in the same manner as in Example 24, without adding the dendritic polyester and the transesterification inhibitor, at a kneader temperature of 240 ° C and a spinning temperature of 245 ° C. The spinning pack pressure at this time was 17 MPa. Since the spinning temperature was higher than that of polylactic acid, the generation of decomposition gas was remarkable and the working environment was deteriorated.

Example 25
PEN having an intrinsic viscosity of 0.75 dL / g was dried, blended and melt-spun as in Example 6. At this time, the kneader temperature was 290 ° C., the spinning temperature was 290 ° C., the discharge rate was 20 g / min, the spinneret was φ0.60 mm, 10 holes, and the spinning speed was 1350 m / min. The spinning pack pressure at this time was 5.8 MPa, and the effect of improving fluidity could be confirmed. U% of the obtained high-speed spinning fiber was 0.95% Comparative Example 13
Melt spinning was carried out in the same manner as in Example 25 without adding the dendritic polyester and the transesterification inhibitor, at a kneader temperature of 295 ° C. and a spinning temperature of 300 ° C. The spinning pack pressure at this time was 6.8 MPa.

Example 26
Nylon 66 having a relative viscosity of 3.8 was dried, blended and melt-spun as in Example 6. At this time, the kneader temperature was 290 ° C., the spinning temperature was 290 ° C., the discharge rate was 33.5 g / min, the spinneret was φ0.30 mm, 18 holes, and the spinning speed was 1500 m / min. The spinning pack pressure at this time was 12.5 MPa, and the effect of improving fluidity could be confirmed. U% of the obtained fiber was 0.95% Comparative Example 14
Melt spinning was carried out in the same manner as in Example 26 except that the dendritic polyester and the transesterification inhibitor were not added and the kneader temperature was 295 ° C. and the spinning temperature was 295 ° C. The spinning pack pressure at this time was 16.5 MPa.

Diagram showing the relationship between spinning temperature and spinning pack pressure Diagram showing the relationship between birefringence and elastic modulus

Claims (8)

  A structural unit composed of an aromatic oxycarbonyl unit (P), an aromatic and aliphatic dioxy unit (Q), and an aromatic dicarbonyl unit (R) and a trifunctional or higher functional organic residue (B), and From a polymer blend in which a dendritic polyester having a B content in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester is blended with a thermoplastic matrix polymer in an amount of 0.1 to 10 wt%. A fiber comprising 0.1-5% of Worcester spots on the fiber.   The fiber according to claim 1, wherein the thermoplastic matrix polymer is polyester.   The fiber according to claim 1 or 2, having an elastic modulus of 110 to 2000 cN / dtex.   The fiber according to claim 1 or 2, having an elastic modulus of 50 cN / dtex or more and less than 110 cN / dtex.   The fiber according to any one of claims 1 to 4, comprising 0.01 to 1 wt% of a transesterification inhibitor with respect to the entire polymer blend obtained by blending a dendritic polyester with a matrix polymer.   The fiber according to any one of claims 1 to 3 and 5, wherein the fiber is a monofilament.   A mixed yarn in which the fiber according to any one of claims 1 to 2 and 4 is used as a core yarn.   The fiber product which used the fiber of any one of Claims 1-7 for at least one part.

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