JP5298477B2 - Block polyetheramide resin composition, method for producing the same, and fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blocked polyether amide resin composition and its production method imparting excellent electricity controllability to synthetic fibers and suppressing severance of spun yarns. <P>SOLUTION: The blocked polyether amide resin composition contains organic sulfonate of alkali metal and a hindered phenol-based compound, in which the difference between the amount of water-soluble component in the composition and the amount of the organic sulfonate of alkali metal is 14.5 mass% or below. The production method comprises a process in which an inert gas is allowed to flow through in an amount no less than 3 vol% of the volume of a polymerizing device per minute under stirring when the blocked polyether amide resin composition is polymerized. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a block polyetheramide resin composition and a method for producing the same. More specifically, the present invention relates to a block polyetheramide resin composition capable of imparting excellent antistatic properties to synthetic fibers and a method for producing the same.

  Synthetic fibers typified by polyamide and polyester have excellent physical and chemical properties, but are hydrophobic and have high electrical insulation properties, so that they can easily be charged with static electricity by friction and the charge does not leak easily. As a result, it has a great disadvantage that various obstacles occur. That is, when removing and attaching clothes made of these synthetic fibers, a strong discharge sound is generated by electrostatic discharge, clothes are stuck to the human body due to static electricity on the clothes, and dust and dirt in the air are sucked. This often promotes soiling of clothing and makes the wearer feel very uncomfortable.

  Conventionally, many proposals have been made to improve the antistatic properties of synthetic fibers. However, since this defect is closely related to the excellent properties of synthetic fibers, it is considered difficult to fundamentally solve them. It was done.

For example, a method of adding a polyalkylene ether during melt spinning of a polyester or a method of treating a knitted fabric with an antistatic agent has been proposed, but these methods have insufficient antistatic performance or antistatic performance by washing. There is a problem that it is easily reduced, and the excellent characteristics and texture inherent to the synthetic fiber are lost. There has also been proposed a method in which a small amount of block polyether ester amide is added to polyester fiber and mixed spinning. According to this method, the antistatic property can be imparted without impairing the excellent physical and chemical properties inherent to the synthetic fiber, but the antistatic effect is still not fully satisfactory, and particularly the polyester fiber. Then, the tendency was big. In order to solve these problems, there has been proposed a method (Patent Document 1) in which an alkali metal salt of an organic sulfonic acid is adsorbed beforehand on a block polyether amide, and then mixed with polyester and spun. However, the organic sulfonic acid alkali metal salt is not uniformly adsorbed to the block polyether amide, and the dispersion in the polymer is non-uniform, so that the quality of the resulting fiber varies widely. The alkali metal salt adsorption process is complicated and requires extra capital investment. In addition, a method of adding a hindered phenol compound to polyester (Patent Document 2) is known for the purpose of colored spinning when mixing and spinning polyester and block polyether amide. According to this method, fiber coloring is performed. Although it is suppressed, the antistatic property of the obtained fiber has not been fully satisfactory. In order to further improve these drawbacks, a method for improving the antistatic property by adding an alkali metal salt of an organic sulfonic acid and a hindered phenol compound at the time of polymerization is disclosed (Patent Document 3). When the block polyetheramide resin composition obtained by this method is used as an antistatic agent for polyester fibers, the antistatic property of the fibers obtained is certainly improved, but there is a problem that yarn breakage frequently occurs during spinning. In particular, when the addition rate of the block polyether amide composition was increased, the influence was remarkable.
Japanese Patent Publication No. 47-27805 Japanese Patent Publication No. 48-15208 JP-A-53-80497

  Therefore, the present inventors have improved the conventional drawbacks as described above, imparted excellent antistatic properties to synthetic fibers such as polyester fibers, and stabilized spinning processability with little spun yarn breakage. It is an object of the present invention to provide a simple block polyetheramide resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the water-soluble component in the block polyetheramide resin composition correlates closely with the spun yarn breakage. Furthermore, the present inventors have found that the water-soluble component can be suppressed within a specific range by optimizing the polymerization conditions.

That is, the present invention is a block polyether amide resin composition containing an alkali metal salt of an organic sulfonic acid and a hindered phenol compound, wherein the amount of water-soluble component in the composition and the amount of the alkali metal salt of the organic sulfonic acid. The present invention relates to a block polyetheramide resin composition used as an antistatic agent for a synthetic fiber having a difference of 14.5% by mass or less, and an alkali metal salt of an organic sulfonic acid and a hindered material as compared with a raw material monomer system or polymerization system The block polyether amide resin, wherein an inert gas is allowed to flow in an amount of 3 to 15 % by volume of an inner volume of a polymerization tank of a polymerization apparatus per minute with stirring when a phenolic compound is added for polymerization. The present invention relates to a method for producing a composition, and further the block polyetheramide resin composition and polyester This invention relates to a fiber obtained by mixing and spinning with a resin.

  The block polyether amide resin composition of the present invention thus obtained is obtained by dispersing an alkali metal salt of an organic sulfonic acid and a hindered phenol compound in an extremely uniform and finely dispersed manner in a fiber-forming polymer such as a polyester resin. On the other hand, excellent antistatic properties can be imparted, and there is little yarn breakage during spinning, and excellent productivity is exhibited.

  The block polyether amide resin used in the present invention is a block copolymer having a structure in which a polyalkylene ether chain and a polyamide chain are linearly bonded, and the block polyether amide resin is obtained by the following method. Can be manufactured.

A: In the presence of a polyalkylene ether having an amino group at the terminal or an organic acid salt thereof, for example, lactams, ω-amino acids, or diamine and a polyamide-forming monomer such as dicarboxylic acid are polycondensed. The monomer configuration is, for example, as follows.
A-1: at least one selected from ω-amino acids, lactams, diamines and dicarboxylic acid salts A-2: a diamine having a polyalkylene ether structure A-3: if necessary, an A-2 component C4-C20 dicarboxylic acid which forms a salt.

B: The polyamide-forming monomer is polycondensed in the presence of a polyalkylene ether having a carboxyl group at the terminal or an organic amine salt thereof. The monomer configuration is, for example, as follows.
B-1: ω-amino acid, lactam, at least one selected from salts of diamine and dicarboxylic acid B-2: dicarboxylic acid having polyalkylene ether structure B-3: component B-2 if necessary And a diamine having 4 to 20 carbon atoms which forms a salt.

C: The polyamide-forming monomer is polycondensed in the presence of an amino group, a carboxyl group, or a polyalkylene ether having both an amino group and a carboxyl group at the terminal. The monomer configuration is, for example, as follows.
C-1: at least one selected from ω-amino acid, lactam, diamine and dicarboxylic acid salt C-2: monoamine, monocarboxylic acid or ω-amino acid having a polyalkylene ether structure.

  The block copolymer used in the present invention may use an appropriate combination method other than the above methods, and other known block copolymer production methods. However, it is preferable to employ the above-mentioned method A, particularly in the presence of a salt comprising a polyalkylene ether having an amino group at both ends and an aliphatic or aromatic dicarboxylic acid, for example, lactams, ω-amino acids, or It is advantageous to polycondensate a diamine with a polyamide-forming monomer such as a dicarboxylic acid.

  Specific examples of salts of ω-amino acids, lactams, diamines and dicarboxylic acids which are components of A-1, B-1 and C-1 include, for example, ω-aminoundecanoic acid, ω-aminoenanthic acid, ω-aminoberconic acid. , Ω-aminocaproic acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or lactams such as ε-caprolactam, enantolactam, capryllactam, laurolactam and hexamethylenediamine-adipate, hexamethylene Diamines such as diamine-sebacate and hexamethylenediamine-isophthalate and dicarboxylates are used, among which caprolactam and / or hexamethylenediamine-isophthalate are preferably used.

  A monomer having a polyalkylene ether structure which is a component of A-2, B-2 and C-2 can be obtained, for example, by converting the terminal of polyalkylene glycol into an amine and / or a carboxylic acid. Specific examples of the polyalkylene glycol used at this time include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polybutylene glycol and the like. These can be obtained by polymerizing one or more selected from ethylene oxide, propylene oxide, and butylene oxide. The molecular weight of these polyalkylene glycols is usually 1000 or more, preferably 3000 to 8000. Of these, polyethylene glycol is preferably used.

  Specific examples of the dicarboxylic acid having 4 to 20 carbon atoms as component A-3 include aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecadicarboxylic acid, or terephthalic acid, isophthalic acid, phthalic acid Examples thereof include aromatic dicarboxylic acids such as acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and diphenyl-4,4′-dicarboxylic acid. Among them, adipic acid is preferably used.

Specific examples of the diamine having 4 to 20 carbon atoms as the B-3 component include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane. 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, Aliphatic alkylenediamines such as 1,14-diaminotetradecane, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-amino Cyclohexyl) propane, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, etc. Diamines, meta-xylylenediamine, and aromatic diamines such as p-xylylenediamine.

  Polyamide-forming monomer component (above A-1, B-1 or C-1) and polyether-containing monomer component (above A-2 and 3, B-2 and 3, or C-2) in block polyetheramide resin The mass ratio is preferably 70 to 30 to 30 to 70, more preferably 60 to 40 to 40 to 60, and most preferably 55 to 45 to 45 to 55.

  These monomer components are usually introduced into the polymerization apparatus as a simple substance, an aqueous solution and / or a water slurry, but a method that is easy to handle may be adopted in consideration of the melting point, water solubility, transportation method, and weighing method. In view of ease, it is preferably introduced as an aqueous solution and / or water slurry. At this time, other additive components can be added simultaneously. It is also possible to perform polymerization by mixing, preheating, prepolymerizing and / or concentrating each component or in a combination of two or more and then mixing all of them. When an aqueous solution and / or water slurry is used as the introduction method, a method in which the monomer component is concentrated to a concentration of about 80% and then introduced into the polymerization apparatus is preferably employed in order to make the equipment scale appropriate.

  The alkali metal salt of an organic sulfonic acid and a hindered phenol compound in the present invention can be added to the block polyether amide forming component both together or separately. The polymerization is preferably performed before completion of the polymerization, and is particularly preferably added to the monomer of the polyamide-forming component, the concentrate of the aqueous monomer solution or the polymerization reaction product before the polymerization is completed. The most preferred method of adding the additive is to first make a 20 to 40% by weight aqueous solution of an alkali metal salt of an organic sulfonic acid, and add or dissolve the hindered phenolic compound to the block polyether amide-forming monomer. It is. In addition, since many alkali metal salts of organic sulfonic acid have foaming properties, there may be a problem that the system foams during the concentration or polymerization of the monomer component and the internal liquid flows out of the system. In this case, an antifoaming agent such as silicone oil can be added to the system.

  Specific examples of the organic sulfonic acid forming the organic sulfonic acid include alkyl benzene sulfonic acids such as dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, and nonyl benzene sulfonic acid. Among them, dodecyl benzene sulfonic acid is preferably used. . Examples of the alkali metal include sodium and potassium. As the metal salt, sodium dodecylbenzenesulfonate is particularly preferably used.

  Specific examples of the hindered phenol compound include 1,3,5-trimethyl-2,4,6 tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene or N, N′-hexa. Methylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, or 3,5 -Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6- Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) ) -Isocyanurate, octylated diphenylamine, etc., among which 1,3,5-trimethyl-2,4,6tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene is preferred. Used.

  The addition amount of the alkali metal salt of the organic sulfonic acid is usually about 1 to 10% by mass with respect to the total amount of raw materials of the block polyether amide resin composition, and the most preferable antistatic property is given in the range of 3 to 7% by mass. Performance is obtained. However, the addition rate of the organic metal sulfonic acid alkali metal salt can be appropriately increased or decreased depending on the blending ratio of the block polyether amide composition to the final product and the required antistatic performance, considering the other quality of the final product. It is preferable to keep the addition rate as small as possible.

  Further, the addition rate of the hindered phenolic compound can be appropriately increased or decreased according to the quality required for the final product, as described above, but is about 1 to 10% by mass with respect to the total amount of raw materials of the block polyetheramide resin composition, The range of 3 to 7% by mass is particularly preferable, and if it is less than 1% by mass, the antistatic property-imparting performance of the composition cannot be improved synergistically.

  In addition to the alkali metal salts of organic sulfonic acids and hindered phenol compounds, the block polyether amide resin composition of the present invention includes viscosity stabilizers, matting agents, anti-coloring agents, heat resistance agents, pigments, and the like. These additives may be added at any time, and the timing of their addition is selected from any time before, during and after polymerization of the composition.

  In the block polyetheramide resin composition of the present invention, it is extremely important to suppress the amount of water-soluble components, and this can prevent yarn breakage when spinning by mixing with a thermoplastic resin. Constituent components of the water-soluble component are not clarified, but impurities in the unreacted monomer, low polymer, polyether-containing monomer (A-2 and 3, B-2 and 3, or C-2) And alkali metal salts of organic sulfonic acids. Of these, the alkali metal salt of organic sulfonic acid is not involved in yarn breakage during spinning, so the amount of water-soluble component and the amount of alkali metal salt of organic sulfonic acid substantially affect the yarn breakage. It is a component equivalent to the difference of. The difference between the amount of the water-soluble component and the alkali metal salt of the organic sulfonic acid must be 14.5% by mass or less, and most preferably 13.5% by mass or less. If it exceeds 14.5% by mass, yarn breakage during spinning cannot be suppressed. The lower limit is not particularly limited and is preferably lower. However, the lower limit is actually limited by the influence of polymerization equilibrium and impurities in the polyether-containing monomer. It is possible to reduce the amount of water-soluble components in the composition by performing a hot water extraction operation that is generally performed with nylon 6, but it also elutes alkali metal salts of organic sulfonic acids. Therefore, it cannot be applied to the block polyetheramide resin composition of the present invention. In the present invention, the amount of the water-soluble component and the amount of the alkali metal salt of the organic sulfonic acid are values measured by the method described later.

  The block polyether amide resin composition having the above characteristics can be produced by the following method.

  That is, when the block polyetheramide resin is polymerized, an inert gas is circulated while stirring the polymerization reaction system, and the circulated amount is 3% by volume or more of the internal volume of the polymerization tank of the polymerization apparatus per minute. The volume is preferably 5% by volume or more, and most preferably 6% by volume or more. This can suppress the amount of water-soluble components in the block polyetheramide resin composition at the completion of polymerization. Although the mechanism is not clear, it is estimated that impurities in the polyether-containing monomer and the like are discharged out of the polymerization apparatus together with the vapor of the condensed water. The upper limit of the inert gas flow rate is not particularly limited, but usually 15% by volume or less is adopted in consideration of economy and effects. In addition, the capacity | capacitance of the inert gas said by this invention points out the capacity | capacitance under 25 degreeC and atmospheric pressure.

  The internal volume of the polymerization tank in the above is a total value of the liquid phase part and the gas phase part (up to the so-called main body nozzle) of the polymerization tank main body, and the internal volume of incidental equipment such as other pipes, coolers, valves, etc. Not included.

  Examples of the inert gas include nitrogen, helium, argon, and neon. Nitrogen is preferable because it is easily available industrially and is inexpensive.

  The polymerization method is not particularly limited, and a usual known polymerization method of polyamide, for example, a normal pressure polymerization method often used for nylon 6 or a pressure polymerization method used for nylon 66 or the like is batch type, continuous. Can be adopted regardless of the formula.

  In any of the polymerization methods in the production method of the present invention, an inert gas is circulated while stirring the liquid phase part of the polymerization tank during the polymerization, thereby efficiently removing heat transfer, condensed water and the like. Can be done. The rotation speed of the stirrer is usually about 10 to 200 rpm, preferably about 10 to 150 rpm, and most preferably about 10 to 100 rpm. The shape of the agitating blade is not particularly limited, but disk turbine type, inclined paddle type, propeller type, anchor type, helical ribbon type, etc. are generally adopted, but since it is a system with high liquid viscosity, it is inclined Paddle type, anchor type and helical ribbon type are preferably used. It is preferable to start the circulation of the inert gas from the time of returning to normal pressure in the case of pressure polymerization, and from the beginning in the case of normal pressure polymerization.

  The polymerization is generally carried out at a normal pressure of 210 ° C. to 330 ° C. over about 4 to 30 hours, and the molten polymer discharged from the polymerization apparatus is cooled and cut into pellets.

  Alkali metal salts of organic sulfonic acids are usually water-soluble, and when the discharge polymer is introduced into water, the additive is eluted, which is not preferable. In this case, for example, the discharge polymer is placed on a metal endless belt cooled with a refrigerant. It is preferable to adopt a means that guides and cools indirectly with a refrigerant, and if necessary, blows cold air onto the polymer surface to forcibly cool and cut as it is.

  The block polyetheramide resin composition of the present invention can be used by mixing and spinning with a thermoplastic resin that is fiber-forming and melt-spinnable. Examples of such thermoplastic resins include polyamide resins and polyester resins. Specific examples of the polyamide resin include, for example, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, a polycondensate of dicarboxylic acid and diamine, and specifically nylon 6, nylon 46, nylon 56, Nylon 66, Nylon 610, Nylon 612, Nylon 11, Nylon 12, and other aliphatic polyamides, poly (metaxylene adipamide), poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide), poly (tetra Methylene isophthalamide), polynonane methylene terephthalamide, and aliphatic-aromatic polyamides such as poly (methylpentamethylene terephthalamide), and copolymers and mixtures thereof. Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polybutylene naphthalate, and poly 1,4-cyclohexylenedimethylene terephthalate. Among them, polyethylene terephthalate is preferable. Used for.

  The block polyetheramide resin composition obtained as described above is mixed with a thermoplastic resin such as a polyester resin and then melt-spun. The total amount of the block polyetheramide resin, the alkali metal salt of organic sulfonic acid and the hindered phenolic compound relative to the thermoplastic resin is usually 0.1 to 5% by mass, preferably 0.3 to 3% by mass, most preferably It mix | blends so that it may become 0.5-1.5 mass%. If the amount is less than 0.1% by mass, the antistatic property of the obtained fiber is not sufficient, and if it exceeds 5% by mass, not only the antistatic effect is further improved, but the color tone of the fiber is deteriorated.

  As a method of making a thermoplastic resin contain a polyetheramide resin composition and making it into fibers, each of them is uniformly mixed in a pellet state and then supplied to a melt spinning machine to make fibers, or each is melted separately Later, it is possible to appropriately select a method in which the fibers are dispersed by a static mixer or the like and then discharged from the die to form fibers.

  In the present invention, it is preferable that the polyetheramide resin composition is uniformly dispersed in the thermoplastic resin, and a continuous and independent streaky dispersed phase is formed in the fiber length direction. As a method of uniformly dispersing the polyetheramide resin composition in the thermoplastic resin, in the case where each is uniformly mixed in a pellet state and then supplied to a melt spinning machine to be a fiber, the fiber is supplied to the melt spinning machine. It is important that the previous mixed pellets are uniformly mixed. As a method for uniformly mixing the pellets, each pellet is weighed and then put into the storage tank, and the storage tank is rotated for 1 to 2 hours. If a rotary batch type vacuum dryer usually used for drying pellets is used, it can be easily and uniformly mixed. Further, if pellets in a required ratio are measured in small amounts and supplied to a melt spinning machine, pellets mixed continuously and uniformly can be supplied to produce yarn. Thus, when yarn is produced using mixed pellets, since the pellets are not as fine as powder, the polyetheramide resin composition can be continuous and independent in the fiber length direction. In addition, when the polyetheramide resin composition and the thermoplastic resin are separately melted and then dispersed by a static mixer or the like and then discharged from the die to form fibers, in order to uniformly disperse, five steps It is preferable to use the above static mixer. Further, if the dispersion is too fine, the continuity in the fiber length direction is liable to be impaired, so that the static mixer is preferably 15 stages or less.

  The present invention will be described in more detail with reference to the following examples. The amount of water-soluble components, relative viscosity, specific resistance and operability in the examples are values measured by the following methods.

[Water-soluble component amount (WSC)]
Precisely weigh about 2 g of pellets from which powder has been removed by direct weighing with a direct balance (W1). Place the weighed sample in a 500 ml Erlenmeyer flask, add 300 ml of distilled water with a graduated cylinder, set the cooling tube and immerse in a water bath. After heating and extracting for 6 hours in a state where the water in the water bath is boiled, suction filtration is performed with a 1G-3 glass filter having a known mass. The whole amount of 300 ml of distilled water is used and washed in several batches, then placed in a weighing bottle with a capacity of 100 ml and preliminarily dried with a filter at 75 ° C. for 16 hours in a hot air dryer. Thereafter, the film is dried for 3 hours in a vacuum dryer (80 ± 2 ° C.), cooled to room temperature in a desiccator, and then weighed with a direct balance (W3). Also, from the powder-removed pellet, about 5 g of a moisture measurement sample is taken into a weighing bottle, dried at 85 ° C. for 80 minutes using a hot air dryer, and after calculating the moisture content from the pellet mass before and after drying, The amount of WSC was calculated from the formula. The measurement was performed twice and the average value was adopted.

[Amount of organic sulfonic acid]
The extract at the time of WSC measurement was freeze-dried, and the obtained sample was dissolved in a mixed solvent of acetonitrile / water to prepare a 10% solution. This was subjected to HPLC analysis under the following conditions, and quantified using a calibration curve prepared with a standard (dodecylbenzenesulfonic acid). The measurement was performed twice and the average value was adopted.

Column: Capcellpak NH2
Mobile phase: A = 0.1 M sodium perchlorate, 10 mM phosphate buffer (pH 2.6)
B = acetonitrile
A / B = 40/60
Flow rate: 1.0 ml / min
Detector: UV detection 230 nm
Temperature: 45 ° C.

[Relative viscosity]
About 100 g of sample pellets and crushed dry ice are put into a pulverizer, pulverized for 1 minute, put into 20 mesh and 100 mesh standard sieves, and sieved. The powder sample passing through a 20 mesh standard sieve and on the 100 mesh standard sieve is transferred to a 30 ml weighing bottle and dried for 3 hours under conditions of a temperature of 60 ± 2 ° C. and a pressure of 5 mmHg or less. When drying is completed, the sample is allowed to cool to room temperature in a desiccator, and 0.250 ± 0.001 g of the dried sample is precisely weighed using a chemical balance in a 50 ml conical flask with a stopper. Add chloral hydrate with a concentration of 70% so that the sample concentration is 1 g / 100 ml, and leave it at room temperature (25 ± 10 ° C.) for about 20 minutes. Furthermore, after fixing to a shaker and stirring and dissolving at room temperature for 30 minutes, the relative viscosity was measured with an Ostwald viscometer in a constant temperature water bath maintained at 25.00 ± 0.02 ° C. The measurement was performed twice and the average value was adopted.

[Yarn specific resistance]
The sample is washed for 2 hours in a weakly alkaline aqueous solution of 0.2% anionic surfactant using an electric washing machine, washed with water and dried. Next, the sample was aligned with a fiber bundle having a length (L) of 5 cm and a fineness (D) of 2000 dtex and conditioned at 20 ° C. and 40% RH for 24 hours. The resistance of the sample was measured at 500 V and calculated by the following formula.
ρ = (R × D) / (10 ⁷ × L × d)
ρ: Volume resistivity (Ω · cm)
R: Resistance (Ω)
d: Sample density (g / cm ³ )
D: Fineness (dtex)
L: Sample length (cm)
XX and XX are the target levels of the present invention, and XX is more desirable than XX.
○○: Less than 50 (× 10 ⁸ Ω · cm) ○: 50 to 300 (× 10 ⁸ Ω · cm)
×: Over 300 (× 10 ⁸ Ω · cm).

(Spinning property (number of thread breaks))
The number of yarn breakage when a total of 1,000 kg of polymer was obtained by the method described in the examples was shown. XX and XX are the target levels of the present invention, and XX is more desirable than XX.
○○: No thread breakage ○: Thread breakage 1 to 2 times ×: Thread breakage 3 times or more.

Example 1
Polyethylene glycol is reacted with acrylonitrile in the presence of an alkali catalyst and further subjected to a hydrogenation reaction to synthesize polyethylene glycol diamine (number average molecular weight 4000) with 97% or more of both ends being amino groups, and this and adipic acid Was subjected to a salt reaction by a conventional method to obtain a 45% by mass aqueous solution of polyethylene glycol diammonium adipate.

200.0 kg of the above-mentioned 45% by mass polyethylene glycol diammonium adipate aqueous solution (pure amount: 90.0 kg, ratio to the total polymerization raw material: 42.6% by mass) and 120% by mass of 85% by mass caprolactam aqueous solution in a 2 m ³ concentration canister 0.0 kg (pure amount: 102.0 kg, ratio to the total polymerization raw material: 48.3 mass%), 40 mass% hexamethylene diammonium isophthalate aqueous solution 16.0 kg (pure quantity: 6.4 kg, based on the total polymerization raw material) (Ratio: 3.0% by mass), and the mixture was heated at normal pressure until the internal temperature reached 110 ° C. for about 2 hours and concentrated to about 80% concentration. Subsequently, the concentrated liquid was transferred to a 800 L polymerization tank equipped with a helical ribbon stirring blade (internal volume of the polymerization tank), and heating was started at a stirring speed of 20 rpm while flowing nitrogen at 50 L / min into the polymerization tank. did.

  When the internal temperature reached 120 ° C., 52.8 kg (pure quantity: 10.6 kg, ratio to the total polymerization raw material: 5.0% by mass) of an aqueous solution of sodium dodecylbenzenesulfonate (DBS) having a concentration of 20% by mass and 1, A slurry in which 2.1 kg of 3,5-trimethyl-2,4,6tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330 manufactured by Ciba-Geigy Co., Ltd .; expressed as “IR1330”) was mixed. Then, stirring was started and heating was performed until the internal temperature reached 250 ° C. to complete the polymerization.

After the polymerization is completed, a pressure of 0.7 MPa · G is applied to the can with nitrogen, and the molten polymer is rotated into a belt with a width of about 15 cm and a thickness of 1.5 mm. Endless belt (length 6 m, belt material: stainless steel, back sprayed with water) And cooled, and cut into pellets after cooling, and the WSC amount and relative viscosity of the obtained pellets were measured.
After the pellets and polyethylene terephthalate pellets were dried, they were weighed so that the mixing ratio was 1:99 in terms of mass ratio and supplied to a rotary batch vacuum dryer filled with nitrogen at room temperature and without heating. By rotating for about 1 hour, uniformly mixed mixed pellets were produced.

  The mixed pellets are supplied to a spinning machine, and a molten polymer is discharged at a spinning speed of 1500 m / min by discharging a molten polymer of 36 g / min from a die nozzle (36 holes) under a spinning temperature of 282 ° C., and 40% by mass of a fatty acid ester. An oil agent containing 9% by mass of polyether was applied at 1% by mass with respect to the mass of the fiber to obtain an undrawn yarn of 252 dtex-36 filaments. The number of yarn breaks at this time was measured. The obtained undrawn yarn was drawn and heat set at a drawing temperature of 87 ° C., a heat setting temperature of 145 ° C. and a magnification of 3.0 times to obtain a drawn yarn of 84 dtex-36 filament. The specific resistance of the obtained drawn yarn was measured. These results are shown in Table 1.

(Examples 2 to 7)
The same operation as in Example 1 was performed except that the addition rate of DBS and IR1330 was changed as described in Table 1.

(Comparative Examples 1-11)
As described in Table 1, the same operation as in Example 1 was performed except that the addition ratio of DBS and IR1330 and the amount of nitrogen flowing through the polymerization tank were changed.

  As is apparent from Table 1, the fiber blended with the composition of the present invention having a low WSC content significantly reduced the number of yarn breakage without impairing the antistatic property regardless of the composition ratio.

(Examples 8 to 10, Comparative Examples 12 and 13)
The same operation as in Example 1 was performed except that the addition ratio of DBS and IR1330 shown in Table 2 and the amount of nitrogen flowed into the polymerization tank were used.

  As apparent from Table 2, when the nitrogen flow rate per minute with respect to the polymerization apparatus capacity exceeded 3% by volume, the WSC amount decreased and the yarn breakage also decreased.

Claims (8)

A block polyetheramide resin composition containing an alkali metal salt of an organic sulfonic acid and a hindered phenol compound, wherein the difference between the amount of the water-soluble component in the composition and the amount of the alkali metal salt of the organic sulfonic acid is 14.5 A block polyetheramide resin composition used as an antistatic agent for synthetic fibers having a mass% or less. 2. The block polyether amide resin composition according to claim 1, wherein the alkali metal salt of the organic sulfonic acid is a sodium salt of alkylbenzene sulfonic acid. 3. The hindered phenol compound is 1,3,5-trimethyl-2,4,6tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene. The block polyether amide resin composition described. The block polyetheramide resin composition according to any one of claims 1 to 3, wherein a difference between the amount of the water-soluble component and the amount of the alkali metal salt of the organic sulfonic acid is 13.5% by mass or less. The block polyetheramide resin composition according to any one of claims 1 to 4, which has a unit derived from ε-caprolactam in the main chain. The block polyetheramide resin composition according to any one of claims 1 to 5, which has a unit derived from polyethylene glycol in the main chain. When an alkali metal salt of an organic sulfonic acid and a hindered phenol compound are added to a raw material monomer or polymerization system for polymerization, an inert gas is allowed to flow in the polymerization tank of the polymerization apparatus per minute while stirring. 3-15 and characterized in that through volume% flow method for producing a block polyetheramide resin composition according to any one of claims 1 to 6. A fiber obtained by mixing and spinning the block polyetheramide resin composition according to any one of claims 1 to 6 and a thermoplastic resin.