KR20230015732A - Polyarylene sulfide mono-filament fiber - Google Patents

Abstract

Embodiments relate to novel polyarylene sulfide monofilament fibers, and the polyarylene sulfide monofilament fibers of embodiments can be usefully used as the fibers can achieve high melt viscosity, which has been difficult to obtain in the past, while retaining desirable physical properties.

Description

Polyarylene sulfide monofilament fiber {POLYARYLENE SULFIDE MONO-FILAMENT FIBER}

Embodiments relate to polyarylene sulfide monofilament fibers.

Polyarylene sulfide is an important engineering plastic, and its demand for various applications such as high-durability plastic molded products, electrical products, and textiles is increasing due to its properties such as high heat resistance, chemical resistance, incombustibility, and high strength.

Among them, in particular, in the use of producing monofilament fibers, it is required that the polyarylene sulfide resin used should have high melt viscosity (MV) while retaining physical properties such as excellent elongation strength and elongation rate. A polyarylene sulfide resin that satisfies the above has not been developed.

Currently, polyarylene sulfide is the only polyarylene sulfide sold in large quantities, and its production methods include a solution polymerization method in which paradichlorobenzene and sodium sulfide are polymerized as raw materials in an N-methylpyrrolidone solvent (patented Reference Document 1), there is a melt polymerization method in which a diiodo aromatic compound and a sulfur compound are polymerized at high temperature without using a solvent.

First, the polyphenylene sulfide resin prepared by the solution polymerization method has a high amount of outgas due to the use of a solvent and chlorine contained in raw materials, a high content of inorganic substances such as sodium chloride, and a high content of low molecular weight oligomers. As a result, a separate cleaning process and / or solvent recovery process for removing by-products is required, which requires high energy requirements and burdens the environment, is difficult to manufacture to have a high melt viscosity, and costs for solvent recovery are high. There are limits to increase.

Polyphenylene sulfide resin produced by the melt polymerization method has excellent productivity and cost structure because it is polymerized under high-temperature vacuum conditions without using a solvent, and has a low outgas amount. etc. has an improved effect. However, due to the non-polar terminal group of the resin, it has low reactivity with processing additives, so it is difficult to modify it to have desired properties, and there are limitations in its use and usage. However, it is still difficult to achieve a sufficiently high melt viscosity and has limitations in that it lacks mechanical properties.

On the other hand, in order to suppress the occurrence of thread breakage of polyarylene sulfide fibers, when polyarylene sulfide resin is prepared by melt polymerization, after polymerization, the reaction mixture is heated under reduced pressure or under atmospheric pressure in a non-oxidizing atmosphere to further progress the polymerization reaction. Alternatively, a method of obtaining a polyarylene sulfide resin having a high molecular weight by removing low molecular weight substances by adding a solvent such as NMP at the end of polymerization or after polymerization has been attempted (Patent Document 2). However, since it is difficult to remove disulfide bonds only by heating the polymerization reaction mixture, and only a small amount of low molecular weight substances can be removed only by adding a solvent, there are still limitations in that it is difficult to achieve a sufficiently high viscosity.

US Patent No. 2,513,188 Korean Patent Publication No. 2016-0050047

Therefore, there is an urgent need for polyarylene sulfide monofilament fibers capable of achieving improved melt viscosity while having excellent physical properties such as elongation strength and elongation.

As a result of intensive research to obtain such polyarylene sulfide monofilament fibers, the present inventors have found that a mixed resin comprising a solution-polymerized polyarylene sulfide resin and a melt-polymerized polyarylene sulfide resin has both excellent physical properties and high melt viscosity. It was found that it can be made to do. In particular, it has been found that a mixed resin comprising a polyarylene sulfide resin post-processed with a compatibilizing agent together with a solution polymerized polyarylene sulfide resin can be prepared to achieve high melt viscosity while maintaining superior physical properties.

Therefore, in the embodiments described below, it is intended to provide a novel polyarylene sulfide monofilament fiber and a method for producing the same.

According to one embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized. and a polyarylene sulfide mixed resin composed of a sulfide resin, wherein the polyarylene sulfide mixed resin is compared to an arithmetic mean of a melt viscosity of the first polyarylene sulfide resin and a melt viscosity of the second polyarylene sulfide resin. Monofilament fibers having increased melt viscosity are provided.

According to another embodiment, a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized into the first polyarylene sulfide resin, wherein a terminal group derived from a compatibilizing agent is introduced into the first polyarylene sulfide resin, which is then processed. and a post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound, wherein the post-processed polyarylene sulfide mixed resin comprises the first polyarylene sulfide mixed resin. A monofilament fiber having an increased melt viscosity relative to the arithmetic mean of the melt viscosity of the polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin.

The polyarylene sulfide monofilament fibers of the embodiment have excellent physical properties such as elongation strength and elongation rate, and high viscosity, so that they have excellent processability and abrasion resistance.

Hereinafter, the invention will be described in detail through embodiments. Embodiments are not limited to the contents disclosed below, and may be modified in various forms unless the gist of the invention is changed.

[Polyarylene sulfide blended resin monofilament fibers]

According to the embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized and a polyarylene sulfide mixed resin composed of a resin, wherein the polyarylene sulfide mixed resin has a melt viscosity of the first polyarylene sulfide resin and a melt viscosity of the second polyarylene sulfide mixed resin. A monofilament fiber (hereinafter, polyarylene sulfide blended resin monofilament fiber) having an increased melt viscosity is provided.

According to another embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized. A polyarylene sulfide mixed resin composed of a sulfide resin and having an increased melt viscosity compared to the arithmetic average of the melt viscosity of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide mixed resin preparing the composition; and spinning and/or drawing the composition. A method for producing monofilament fibers is provided.

First polyarylene sulfide resin

The first polyarylene sulfide resin may be prepared by melt polymerization of a composition including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor.

A diiodo aromatic compound means a compound having an aromatic ring and two iodine atoms bonded directly thereto. Diiodo aromatic compounds include diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododiphenyl It may be at least one selected from the group consisting of sulfone, but is not limited thereto.

The aromatic ring of the diiodo aromatic compound is selected from the group consisting of a halo group, a phenyl group, a hydroxyl group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone, and an arylketone, excluding the iodo group. It may be substituted by at least one selected substituent. When the aromatic ring of the diiodo aromatic compound is substituted by the substituent, the diiodo aromatic compound having the aromatic ring substituted with the substituent has a diiodo aromatic ring having an unsubstituted aromatic ring from the viewpoint of crystallinity and heat resistance of the resin. may also be 0.0001 to 5% by weight or 0.001 to 1% by weight based on the aromatic compound. The substitution positions of the two iodo groups present in the diiodo aromatic compound are not particularly limited, but the two substitution positions may be located far from each other in the molecule, and may be para positions or 4,4'- positions.

The amount of the diiodo aromatic compound is 0.5 to 2.0 moles, 0.55 to 1.9 moles, 0.6 to 1.8 moles, 0.65 to 1.7 moles, 0.7 to 1.6 moles, 0.75 to 1.5 moles, or 0.8 to 1.4 moles based on 1 mole of the first sulfur compound. can be included as The diiodo aromatic compound may be, for example, p-diiodobenzene.

The first sulfur compound may be simple sulfur. Simple sulfur means a compound composed of sulfur atoms. Simple sulfur may be at least one selected from the group consisting of S ₈ , S ₆ , S ₄ and S ₂ , and specifically, may be a mixture containing S ₈ and S ₆ that are generally available, but is limited thereto. It doesn't work. The purity, form and particle size of simple sulfur are not particularly limited. For example, the form of simple sulfur may be granular or powdery, which is solid at room temperature (23°C). In addition, the particle diameter of simple sulfur may be 0.001 to 10 mm, 0.01 to 5 mm, or 0.01 to 3 mm, but is not particularly limited thereto.

The polymerization inhibitor may be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction of the first polyarylene sulfide resin. The polymerization inhibitor is a compound capable of introducing at least one functional group selected from the group consisting of -OR, -SR, -COOR, -NHR, -SO ₃ R, and -NHCOR to the main chain terminal of the polyarylene sulfide resin. , wherein each R may independently be a hydrogen group, a metal cation such as sodium or lithium, a halo group, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. The polymerization inhibitor may contain the functional group, and may generate the functional group by a polymerization termination reaction or the like. In addition, the polymerization inhibitor may be a compound that does not contain the above functional group, specifically, diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole , N-cyclohexyl-2-benzothiazolyl sulfenamide, 2- (morpholinothio) benzothiazole and N, N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide selected from It may be at least one kind of compound.

In addition, the polymerization inhibitor may be one or more of the compounds represented by Formulas 1 to 4 below, and specifically may be a compound represented by Formula 1.

[Formula 1]

X ¹ and X ² are each independently a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA ¹ , -SA ² , -COOA ³ , -NA ⁴ A ⁵ , - It is selected from the group consisting of SO ₃ A ⁶ and -NHCOA ⁷ , and A ¹ to A ⁷ are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic phenyl group, and Z ¹ to Z ⁴ are each independently a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms. It is selected from the group consisting of groups, and m ¹ and m ² are each independently an integer of 1 to 3.

When Z ¹ and Z ² are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring. In addition, when Z ³ and Z ⁴ are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.

When m ¹ or m ² is 2 or more, 2 or more X ¹ or X ² bonded to one aromatic ring may be identical to or different from each other. Also, Z ¹ and Z ³ may be the same as or different from each other, and Z ² and Z ⁴ may be the same as or different from each other.

The substituted phenyl group of X ¹ or X ² may have a substituent of -SH or -SS-Ph. In addition, the substituted alkyl group having 1 to 3 carbon atoms and the substituted phenyl group of A ¹ to A ⁷ may have a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group.

Z ¹ and Z ² may be bonded to two adjacent carbon atoms, and Z ³ and Z ⁴ may be bonded to two adjacent carbon atoms.

Also, at least one or two or more of Z ¹ to Z ⁴ may not be hydrogen groups. In addition, at least one of X ¹ and X ² may be selected from the group consisting of -OA ¹ , -SA ² , -COOA ³ , NA ⁴ A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ . Also, for example, when X ¹ and X ² are both hydrogen groups, at least one of a combination of Z ¹ and Z ² or a combination of Z ³ and Z ⁴ may be connected to each other to form a benzene ring.

[Formula 2]

X ³ to X ⁶ are each independently a hydrogen group, a halo group, an alkyl group having 1 to 5 carbon atoms, -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , A ⁸ to A ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R ¹ to R ⁴ are each independently It is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms and an alkoxy group.

At least one of X ³ to X ⁶ may be selected from the group consisting of -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ . In addition, at least one of X ³ to X ⁶ may be -SA ⁹ in which A ⁹ is a hydrogen group.

[Formula 3]

X ⁷ to X ¹² are each independently a hydrogen group, a halo group, an alkyl group having 1 to 5 carbon atoms, -OA ¹⁵ , -SA ¹⁶ , -COOA ¹⁷ , -NA ¹⁸ A ¹⁹ , -SO ₃ A ²⁰ and -NHCOA ²¹ , A ¹⁵ to A ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ are each independently It is an alkylene group of 1 to 5 carbon atoms.

[Formula 4]

X ¹³ is a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA ²² , -SA ²³ , -COOA ²⁴ , NA ²⁵ A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ , and A ²² to A ²⁸ are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group. is selected, W is a halo group, Z ⁵ and Z ⁶ are each independently a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms. It is selected from the group, n is an integer from 1 to 3.

When Z ⁵ and Z ⁶ are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring. When n is 2 or more, 2 or more X ¹³ bonded to one aromatic ring may be the same as or different from each other.

Z ⁵ and Z ⁶ may be bonded to two adjacent carbon atoms. Also, at least one of Z ⁵ and Z ⁶ may not be a hydrogen group. In addition, at least one of X ¹³ may be selected from the group consisting of -OA ²² , -SA ²³ , -COOA ²⁴ , NA ²⁵ A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ .

The substituted phenyl group of X ¹³ may have a substituent of -SH or -SS-Ph. In addition, the substituted alkyl group having 1 to 3 carbon atoms or the substituted phenyl group represented by A ²² to A ²⁸ may have a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group.

In addition, the polymerization inhibitor may be included in an amount of 0.0001 to 0.1 mole, 0.0002 to 0.08 mole, 0.0005 to 0.05 mole, or 0.001 to 0.05 mole based on 1 mole of the first sulfur compound.

Meanwhile, in the melt polymerization, a catalyst may be additionally used. The catalyst may be, for example, a nitrobenzene-based catalyst, and may specifically be at least one selected from the group consisting of 1,3-diiodo-4-nitrobenzene and 1-iodo-4-nitrobenzene, but is not limited thereto. When the catalyst is used, it may be used in an amount of 0.0001 to 0.1 mole, 0.0002 to 0.05 mole, or 0.0005 to 0.01 mole based on 1 mole of the first sulfur compound.

The melt polymerization may be performed under any conditions as long as the polymerization reaction of the composition including the diiodo aromatic compound and the first sulfur compound can be initiated. For example, the melt polymerization may be performed at a temperature of about 180 to 400 ° C, 180 to 350 ° C, or 180 to 300 ° C, and at a pressure of about 0.001 to 500 torr, 0.001 to 450 torr, or 0.001 to 400 torr. . More specifically, the melt polymerization may be carried out under conditions of elevated temperature and reduced pressure. In this case, the temperature is raised and the pressure is decreased under the initial reaction conditions of a temperature of about 180 to 250 ° C. and a pressure of about 50 to 450 torr to perform the final reaction temperature It may be performed for about 0.1 to 30 hours at about 270 to 350° C. and a pressure of about 0.001 to 20 torr. More specifically, melt polymerization may be performed under final reaction conditions of about 280 to 300° C. and about 0.1 to 2 torr of pressure.

Meanwhile, the order of mixing the diiodo aromatic compound, the primary sulfur compound, and the polymerization inhibitor is not particularly limited, but the diiodo aromatic compound, the primary sulfur compound, and the polymerization inhibitor may be simultaneously mixed, or the diiodo aromatic compound And a composition for melt polymerization may be prepared by mixing a polymerization inhibitor with a mixture including the first sulfur compound.

When the polymerization inhibitor is not mixed with the diiodo aromatic compound and the first sulfur compound at the same time, the timing of adding the polymerization inhibitor is not particularly limited, but may be determined in consideration of the target final molecular weight of polyarylene sulfide. For example, about 0 to 30% by weight, 30 to 70% by weight, or 70 to 100% by weight of the diiodine aromatic compound included in the initial reactant may be added at the time when the reaction is exhausted. Alternatively, the polymerization inhibitor may be added when the molecular weight of the polymerization reactant reaches a certain level. For example, the molecular weight of the polymerization reaction product is 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% of the final molecular weight of the target polyarylene sulfide. When % or more, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, the polymerization inhibitor may be added. The molecular weight of the polymerization reactants can be measured, for example, by gel permeation chromatography.

In addition, the composition including the diiodine aromatic compound and the first sulfur compound may be melt-mixed prior to introduction of the polymerization inhibitor. In this case, the catalyst may also be included in the composition in the melt mixing step. The melt-mixing is not particularly limited as long as all of the compositions can be melt-mixed, but may proceed at a temperature of about 130 to 200°C or about 160 to 190°C. When such melt mixing is performed, melt polymerization to be performed later may proceed more easily.

Second polyarylene sulfide resin

The second polyarylene sulfide resin may be prepared by solution polymerization of a dihalo aromatic compound and a second sulfur compound.

The second polyarylene sulfide resin is not particularly limited as long as it is prepared by including solution polymerization of a dihalo aromatic compound and a second sulfur compound. As a commercial production method of such polyarylene sulfide resin, the Macallum process of solution polymerization of p-dichlorobenzene and sodium sulfide in the presence of a polar organic solvent such as N-methyl pyrrolidone (Macallum process) this is known An exemplary process is described in US Patent No. 2,513,188.

The melt polymerization may be performed in the presence of an organic polar solvent. The organic polar solvent is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam , N-propylcaprolactam, N-methylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolinone, N-ethyl-2-pyrrolidinone, N-isopropyl-2-pyrrolidinone , N-isobutyl-2-pyrrolidinone, N-propyl-2-pyrrolidinone, N-butyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-3-methyl -2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-2-piperidone, N-methyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo-hexamethyleneimine , hexamethylphosphate triamide, hexaethylphosphate triamide, tetramethyl urea, 1,3-dimethylethylene urea, 1,3-dimethylethylene urea, 1,3-dimethylpropylene urea, 1-methyl-1-oxosulfolane , 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-methyl-1-oxophosphane, 1-propyl-1-oxophosphane and 1-phenyl-1-oxophosphane It may be at least one selected from the group consisting of. The organic polar solvent may be, for example, N-methylpyrrolidone.

A dihalo aromatic compound means a compound having an aromatic ring and two halo groups directly bonded thereto. Here, the halogen atom of the halo group may be each atom of fluorine, chlorine, bromine, and iodine, and the two halo groups present in the dihalo aromatic compound may be identical to or different from each other. More specifically, both halogen atoms may be chlorine. Dihaloaromatic compounds include, for example, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl It may be at least one selected from the group consisting of ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide and dihalodiphenylketone. The dihalo aromatic compound may be, for example, 1,4-dichlorobenzene, but is not particularly limited thereto.

The second sulfur compound may be at least one selected from the group consisting of an alkali metal sulfide and an alkali metal sulfide-forming compound capable of forming the alkali metal sulfide. In addition, the second sulfur compound may be at least one selected from the group consisting of an alkali metal hydrosulfide and an alkali metal hydrosulfide forming compound. Secondary sulfur compounds include, for example, alkali metal hydrosulfides such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide, and alkali metals such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. It may be a metal sulfide, but is not particularly limited thereto. The alkali metal sulfide-forming compound or alkali metal hydrosulfide-forming compound may be, for example, hydrogen sulfide. An alkali metal hydrosulfide (eg NaSH) or an alkali metal sulfide (eg Na ₂ S) can be produced by blowing hydrogen sulfide into an alkali metal hydroxide (eg NaOH). The second sulfur compound may be at least one selected from the group consisting of an anhydride, a hydrate, and an aqueous solution. The second sulfur compound may be, for example, sodium sulfide hydrate, but is not particularly limited thereto.

In the step of solution polymerization of the dihalo aromatic compound and the second sulfur compound, the second polyarylene sulfide resin further includes lithium chloride (LiCl) in the solution polymerization reaction product including the dihalo aromatic compound and the second sulfur compound. can be manufactured. If the polyarylene sulfide mixed resin is prepared using the second polyarylene sulfide resin prepared using lithium chloride, the melt viscosity can be further improved, and the processability, wear resistance, Tensile strength and/or tensile elongation can be further improved. Although not bound by a specific theory, this effect may be due to the promotion of additional reaction between the disulfide bond of the first polyarylene sulfide resin and the terminal halogen of the second polyarylene sulfide resin due to the excellent reactivity peculiar to lithium. Lithium chloride may be included in the range of 0.01 to 0.9 mol, specifically 0.5 mol, based on 1 mol of the second sulfur compound. The timing of addition of lithium chloride is not particularly limited, but it may be added to the solution polymerization reactant before the reaction starts.

heat stabilizer

The heat stabilizer may be used to prevent the resin from decomposing due to the action of heat and light during the manufacturing process or use of the resin, and in a high temperature environment when mixing or molding the polyarylene sulfide resin with other additives or resins. It is possible to improve the physical properties of the final polyarylene sulfide resin monofilament fiber by minimizing side reactions that occur. Thermal stabilizers include calcium magnesium zinc thermal stabilizers, calcium zinc thermal stabilizers, organotin thermal stabilizers, metal tin thermal stabilizers, barium zinc thermal stabilizers, epoxy zinc thermal stabilizers, magnesium aluminum carbonate thermal stabilizers, and zinc thermal stabilizers. , metal-based heat stabilizers such as lead-based heat stabilizers, and non-metal-based heat stabilizers such as epoxy-based heat stabilizers and organic phosphite-based heat stabilizers. As for the heat stabilizer, commercially available heat stabilizers include CLC-120 of Dubon Co., Ltd., which is a magnesium aluminum carbonate-based heat stabilizer.

In addition, as the heat stabilizer, for example, a primary phenol-based stabilizer, a secondary phosphorus-based stabilizer, and a primary-secondary mixed type stabilizer may be used, and both the primary and secondary stabilizers have a high molecular weight, or when staying at a high temperature, the corresponding It is desirable that the material has good thermal stability. The primary phenolic stabilizer may include a polyhydric phenolic compound having steric hindrance. The polyhydric phenol-based compound may be a polyhydric alcohol and a plurality of esterification products of carboxylic acids having a phenol group, and the benzene ring of the phenol group may be substituted with an alkyl group having 2 to 10 carbon atoms having a steric hindrance such as a tert-butyl group. there is. In this regard, preferred stabilizers include ADEKA's AO-60 and AO-80, Chemtura's Ultanox627A, Doverphos S9228, and the like.

Polyarylene Sulfide Blended Resin Monofilament Fiber

The polyarylene sulfide blended resin monofilament fiber includes a polyarylene sulfide blended resin composed of a melt-polymerized first polyarylene sulfide resin and a solution-polymerized second polyarylene sulfide resin; and optionally a heat stabilizer. The heat stabilizer is as described above.

Monofilament fibers, unlike multifilament fibers, mean fibers formed from one filament fiber. The monofilament fibers of the present specification have an average aspect ratio, that is, an average fiber length/fiber diameter of, for example, 100 It can be ideal, and theoretically it can be infinite. In addition, the monofilament fiber of the present specification may have an average fineness of about 800 to about 1,000 denier, but may have a different average fineness depending on the application. For example, in the case of wig yarn use, it may have an average fineness of about 200 denier, in the case of cable sleeve use, it may have an average fineness of about 800 to about 1,000 denier, PMC (paper machine clothing) use In the case of, it may have an average fineness of about 2,500 to about 4,000 denier.

Such monofilament fibers may be produced by preparing a polyarylene sulfide resin composition and spinning and/or drawing the prepared composition. A specific composition of the polyarylene sulfide resin composition may be set to be the same as that of the final monofilament fiber.

Specifically, the spinning step may be performed by melt spinning the polyarylene sulfide resin composition, and may be performed using a commonly used melt spinning apparatus, for example, a single-screw or twin-screw extruder-type spinning machine.

The temperature in the spinning step is preferably as low as possible while being a temperature sufficient to melt the polyarylene sulfide resin from the viewpoint of suppressing gelation. For example, the spinning process may be performed under the condition that the temperature of the polyarylene sulfide resin discharged from the nozzle is 250 to 340° C. or 270 to 320° C., and may be performed under a nitrogen atmosphere.

As the spinneret, a spinneret commonly used for melt spinning may be used. For example, a nozzle having a discharge aperture of 0.1 to 1.5 mmφ and a discharge hole depth of about 0.1 to 10.0 mm can be used. The cross-sectional shape of the fiber during spinning is not particularly limited, and may be a normal circular cross-section, triangular cross-section, rectangular cross-section, Y-shaped cross-section, cross-section, C-shaped cross-section, hollow cross-section, or typical cross-section.

The fibers discharged from the spinneret are generally cooled and wound by exposure to wind at a wind speed of 5 to 100 m/min after discharge. In this process, an emulsion may be added and used as a bundling agent. The winding speed may be 10 to 5,000 m/min.

The process method is to obtain monofilament undrawn yarn (UDY) by spinning the polyarylene sulfide resin composition at low speed, or to obtain monofilament partially oriented yarn (POY) by spinning the polyarylene sulfide resin composition at high speed. obtaining; winding the monofilament undrawn yarn or the monofilament partially drawn yarn; It may include a step of obtaining a monofilament fully drawn yarn (FDY) by drawing the wound monofilament undrawn yarn or monofilament partially drawn yarn. Alternatively, the method may include a step of obtaining a draw-textured yarn by inputting the wound unstretched yarn, partially stretched yarn, or fully drawn yarn into a twisting machine to twist and draw the yarn.

In some embodiments, the stretching and twisting may be performed at a stretching ratio of 2.5 to 5.5 times. For example, the monofilament fiber may be stretched 2.5 to 5.5 times before and after the stretching and twisting. In this case, the stretching strength of monofilament fibers can be improved. For example, the tensile strength of the monofilament fibers drawn and/or twisted at the draw ratio may be 3.0 g/de' or more, preferably 3.2 g/de' or more, 3.3 g/de' or more, or 3.6 g/de' or more. de` or more, 3.7 g/de` or more, or 3.8 g/de` or more.

Alternatively, in the spinning step, the polyarylene sulfide resin composition is melt-spun through a spinneret to form a filament, and then cooled and solidified through a water-cooled cooling facility and an air-cooled cooling facility installed directly under the spinneret, and a hot water bath at a temperature higher than Tg. It may be carried out including the step of manufacturing monofilament in a single process through a single equipment that is heat-set after stretching through.

In addition, the polyarylene sulfide blended resin monofilament fibers contain 3% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more of the polyarylene sulfide blended resin based on the total weight of the monofilament fibers. It may include at least 90% by weight, at least 95% by weight, or at least 97% by weight.

In addition, the polyarylene sulfide blended resin monofilament fibers may include 3 wt% or less or 0.01 to 3 wt% of a heat stabilizer based on the total weight of the monofilament fibers, specifically, 0.01 wt% or more or 0.05 wt%. It may contain more than 2% by weight, or less than 2% by weight, less than 1% by weight or less than 0.5% by weight.

Meanwhile, the polyarylene sulfide mixed resin is composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin described above. The polyarylene sulfide mixed resin may have an increased melt viscosity compared to an arithmetic mean of melt viscosities of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin.

Specifically, the polyarylene sulfide mixed resin is the arithmetic mean ( _{( η m} + melt viscosity of 105 to 400% based on η _s )/2). More specifically, the melt viscosity of the polyarylene sulfide mixed resin is 105 to 350%, 105 to 300%, 105 to 250%, 105 to 230%, 105 to 200%, 110 to 400%, 110 to 350% on the same basis. %, 110 to 300%, 110 to 250%, 110 to 230%, 110 to 200%, 130 to 350%, 130 to 300%, 130 to 250%, 130 to 230%, 130 to 200%, 150 to 350 %, 150 to 300%, 150 to 250%, 150 to 230%, 150 to 200%, 160 to 350%, 160 to 300%, 160 to 250%, 160 to 230%, 160 to 200%, 170 to 350 %, 170 to 300%, 170 to 250%, 170 to 230% or 170 to 200%.

In addition, the polyarylene sulfide mixed resin has a melt viscosity of 5,500 to 8,000 Pa s, 5,500 to 7,500 Pa s, 5,500 to 7,000 Pa s, 6,000 to 8,000 Pa s, 6,000 to 7,500 Pa s, or 6,000 to 7,000 Pa s. It may be Pa·s.

Solution polymerized polyarylene sulfide resin prepared by solution polymerization of a dihalo aromatic compound and a sulfur compound has excellent physical properties such as high mechanical strength, but high melt viscosity due to high outgas volume and high inorganic content and low molecular weight oligomer content. It has the disadvantage of being difficult to achieve. On the other hand, the melt polymerized polyarylene sulfide resin, which is prepared by melt polymerization of a mixture containing a diiodo aromatic compound, a sulfur compound and a polymerization inhibitor, has a remarkably low outgas amount, but due to manufacturing characteristics, the disulfide bonds included in the polyarylene sulfide resin It acts as a fragile structure, so it is still difficult to achieve a sufficiently high melt viscosity and has the disadvantage of poor mechanical properties.

However, the present inventors have surprisingly found that a polyarylene sulfide mixed resin having significantly improved melt viscosity can be prepared by mixing the solution polymerized polyarylene sulfide resin and the melt polymerized polyarylene sulfide resin. Furthermore, the polyarylene sulfide mixed resin may have physical properties superior to those of the solution polymerized polyarylene sulfide resin, while the amount of outgas is as low as that of the melt polymerized polyarylene sulfide resin.

The increase in the melt viscosity of the mixed resin may be achieved by a reaction between the first polyarylene sulfide resin and the second polyarylene sulfide resin, although not bound by a specific theory. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved and further reacts with the terminal halogen of the second polyarylene sulfide. can do. Accordingly, the disulfide bond, which is a weak structure of the first polyarylene sulfide, is removed, the halogen of the second polyarylene sulfide is additionally removed, and the melt viscosity can be greatly increased.

Mixing of the first polyarylene sulfide resin, the second polyarylene sulfide resin and/or the heat stabilizer may be performed through melt mixing. Melt mixing may be performed under any conditions as long as the first polyarylene sulfide resin and the second polyarylene sulfide resin can be melted. For example, melt mixing may be performed in a single-screw or twin-screw kneading extruder, polymerization reactor, kneader reactor, or the like. More specifically, melt mixing may be performed in a twin-screw extruder, and may be performed at a temperature of 280 to 330°C, preferably 290 to 310°C. At this time, the discharge amount of the resin component may be 5 to 600 kg / hr at a rotation speed of 100 to 450 rpm, and may be adjusted to 100 to 250 kg / hr in consideration of dispersibility. During the mixing, degassing is performed in a mixer or reactor equipped with a vacuum line, thereby producing a polyarylene sulfide mixed resin having a further reduced amount of outgas.

The polyarylene sulfide mixture resin may include 1 to 99.9% by weight of the first polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixture resin, and more specifically, 10 to 90% by weight, 10 to 99.9% by weight 80 wt%, 10 to 70 wt%, 10 to 60 wt%, 10 to 50 wt%, 10 to 40 wt%, 20 to 90 wt%, 20 to 80 wt%, 20 to 70 wt%, 20 to 60 wt% %, 20 to 50%, 20 to 40%, 30 to 90%, 30 to 80%, 30 to 70%, 30 to 60%, 30 to 50% or 30 to 40% by weight can do.

In addition, the polyarylene sulfide mixed resin may include 1 to 99.9% by weight of the second polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin, more specifically 10 to 90% by weight, 10 to 80% by weight, 10 to 70% by weight, 10 to 60% by weight, 20 to 90% by weight, 20 to 80% by weight, 20 to 70% by weight, 20 to 60% by weight, 30 to 90% by weight, 30 to 80 wt%, 30 to 70 wt%, 30 to 60 wt%, 40 to 90 wt%, 40 to 80 wt%, 40 to 70 wt%, 40 to 60 wt%, 50 to 90 wt%, 50 to 80 wt% %, 50 to 70% by weight, 50 to 60% by weight, 60 to 90% by weight, 60 to 80% by weight or 60 to 70% by weight.

Alternatively, the polyarylene sulfide mixed resin may contain the first polyarylene sulfide resin and the second polyarylene sulfide resin in a ratio of 0.5:9.5 to 9.5:0.5, 1:9 to 9:1, 2:8 to 9:1, 3:7 to 9:1, 1:9 to 8:2, 2:8 to 8:2, 3:7 to 8:2, 1:9 to 7:3, 2:8 to 7:3, 3: 7 to 7:3, 1:9 to 6:4, 2:8 to 6:4, 3:7 to 6:4, 1:9 to 5:5, 2:8 to 5:5 or 3:7 to It may be included in a weight ratio of 5:5.

In some embodiments, the polyarylene sulfide mixed resin may include 1.7% by weight or less of disulfide bonds based on the total weight. In this case, the polyarylene sulfide mixed resin may have improved processability and good cavity balance. Preferably, the disulfide bonds may be included in an amount of 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, or 1.3 wt% or less, and 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, or 0.6 wt%. may include more than

On the other hand, the nonlinear index of the polyarylene sulfide mixed resin is 0.12 to 0.33, 0.12 to 0.30, 0.12 to 0.27, 0.12 to 0.24, 0.12 to 0.23, 0.12 to 0.18, 0.13 to 0.33, 0.13 to 0.30, 0.13 to 0.27, 0.13 to 0.27. 0.24, 0.13 to 0.23 or 0.13 to 0.18. By adjusting the nonlinearity index within this range, it is possible to make the polyarylene sulfide mixed resin have improved processability and good cavity balance. The nonlinearity index can serve as an index for the molecular structure of the object to be measured, such as molecular weight or linear chain, branching, and crosslinking. Usually, when this value is close to 0, it indicates that the molecular structure of the resin is linear, and as this value increases, it indicates that a large number of branched or crosslinked structures are included. In the present specification, the nonlinear index is measured at 300 ° C. with a rotating disk viscometer, and when the viscosity change rate in the shear rate range of 0.03 to 25 s ^-1 is measured by the frequency sweep method, it can be defined through Equation 3 below.

[Equation 3]

Nonlinear index = 1 - (melt viscosity at a shear rate of 17.3 s ^-1 ) / (melt viscosity at a shear rate of 3.22 s ^-1 ).

The polyarylene sulfide mixed resin having the above-mentioned nonlinear index is, for example, in a method of solution polymerization of a mixture for melt polymerization containing a diiodo aromatic compound, a primary sulfur compound, and a polymerization inhibitor, such a polyaryl It is possible to obtain it by making the rene sulfide resin high in molecular weight to some extent.

The molecular weight of the polyarylene sulfide mixed resin can be measured by weight average molecular weight, number average molecular weight, peak peak molecular weight or the like. The weight average molecular weight of the polyarylene sulfide mixed resin is not particularly limited as long as the effects of the present invention are not impaired, but may be 25,000 g / mol or more, 30,000 g / mol or more, or 40,000 g / mol or more in terms of mechanical strength, In terms of cavity balance, it may be 100,000 g/mol or less, 80,000 g/mol or less, or 65,000 g/mol or less. Also, the number average molecular weight may be 1,000 g/mol or more, 5,000 g/mol or more, 7,500 g/mol or more, 9,000 g/mol or more, or 10,000 g/mol or more, and 30,000 g/mol or less, 25,000 g/mol or less. , 20,000 g/mol or less, 15,000 g/mol or less, or 14,000 g/mol or less. If the number average molecular weight is too low, the melt strength is insufficient, so single yarns easily occur in the spinning and / or drawing process, and if it is too high, the die swell phenomenon in the spinneret is severe, resulting in a twisted yarn that bends the extruded strand ( In a more severe case, as knealing occurs in which the extruded strand sticks to the nozzle surface, single yarn may occur, resulting in a poor spinning process.

Further, the peak apex molecular weight may be greater than or equal to 10,000 g/mol, greater than or equal to 15,000 g/mol, greater than or equal to 20,000 g/mol, or greater than or equal to 25,000 g/mol, and less than or equal to 140,000 g/mol, less than or equal to 100,000 g/mol, or less than or equal to 75,000 g/mol. or 70,000 g/mol or less.

The polyarylene sulfide blend resin may have a polydispersity index (PDI) of 2.0 to 6.0, for example, 2.0 to 5.5, 2.0 to 5.0, 2.0 to 4.5, 2.0 to 4.4, 3.0 to 6.0, 3.0 to 5.5, 3.0 to 5.0, 3.0 to 4.5, 3.0 to 4.4, 3.5 to 6.0, 3.5 to 5.5, 3.5 to 5.0, 3.5 to 4.5, 3.5 to 4.4, 4.0 to 4.0, 4.0 to 5.5, 4.0 to 5.0, 4.0 to 4.5 or 4.0 to 4.4 can be The polydispersity index can be calculated as the ratio of the weight average molecular weight to the number average molecular weight.

In addition, the polyarylene sulfide mixed resin may have a melting point of 250 to 300 °C, 260 to 300 °C, 265 to 300 °C, or 270 to 290 °C. In the present specification, the melting point is heated from 30 ° C to 320 ° C at a rate of 10 ° C / min using a differential scanning calorimeter (DSC), cooled to 30 ° C, and then heated again from 30 ° C to 320 ° C. It may be measured while raising the temperature at a rate of 10 °C / min.

The polyarylene sulfide blend resin may include iodine derived from a diiodo aromatic compound, and the iodine content is 1 to 10,000 ppm, specifically, 10 ppm or more, based on the total weight of the polyarylene sulfide blend resin. 50 ppm or more, 100 ppm or more, 200 ppm or more, 300 ppm or more, 400 ppm or more, 500 ppm or more, 600 ppm or more, or 1000 ppm or more, 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less Below ppm, below 4,000 ppm, below 3,000 ppm, below 2,500 ppm, below 2,300 ppm, below 2,270 ppm, below 2,200 ppm, below 2,000 ppm, below 1,900 ppm, below 1,800 ppm, below 1,700 ppm, below 1,600 ppm or below 1,500 ppm can

The polyarylene sulfide mixed resin may include chlorine derived from raw materials used in the manufacture of the second polyarylene sulfide resin, and the chlorine content is 2,500 ppm or less based on the total weight of the polyarylene sulfide mixed resin, 2,300 ppm or less, 2,000 ppm 1,500 ppm or less or 1,000 ppm or less.

The polyarylene sulfide blend resin may include inorganic materials such as Fe, Na, Ca, and Li, and the content of these (metallic) inorganic materials is less than 1,000 ppm and less than 780 ppm based on the total weight of the polyarylene sulfide blend resin. , 700 ppm or less, 600 ppm or less, 500 ppm or less, 400 ppm or less, 300 ppm or less, or 200 ppm or less.

In addition, the polyarylene sulfide mixed resin may have an oligomer content of 0.01 to 5% by weight based on the total weight of the polyarylene sulfide mixed resin, and specifically, 0.10% by weight or more, 0.50% by weight or more, or 0.80% by weight. or 0.90% by weight or more, 3.00% by weight or less, 2.00% by weight or less, 1.50% by weight or less, 1.40% by weight or less, 1.30% by weight or less, or 1.20% by weight or less.

The polyarylene sulfide mixed resin may have a branching index (α) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and may be 1.00 or less, 0.90 or less, 0.80 or less, 0.76 or less, or 0.70 or less. In the present specification, α is calculated through the Mark-Howink equation represented by Equation 4 below. Typically, the closer α is to 1, the linear polymer, and the closer to 0, the branched polymer.

[Equation 4]

[η] = K × M ^α

In the above formula, η is an intrinsic viscosity, M is a weight average molecular weight, and K is a constant.

The polyarylene sulfide mixed resin has a crystallization temperature of 150 to 300 ° C, 150 to 250 ° C, 150 to 240 ° C, 150 to 230 ° C, 150 to 220 ° C, 200 to 300 ° C, 200 to 250 ° C, 200 to 240 ° C, 200 to 230 °C, 200 to 220 °C, 210 to 300 °C, 210 to 250 °C, 210 to 240 °C, 210 to 230 °C or 210 to 220 °C.

The outgas amount of the polyarylene sulfide mixed resin may be 0.001 to 5% by weight, specifically, 0.3 to 1.4% by weight, 0.3 to 1.3% by weight, 0.3 to 1.2% by weight, 0.3 to 1% by weight, 0.4 to 1.4% by weight. 0.4 to 1.3 wt%, 0.4 to 1.2 wt%, 0.4 to 1 wt%, 0.5 to 1.4 wt%, 0.5 to 1.3 wt%, 0.5 to 1.2 wt%, 0.5 to 1 wt%, 0.6 to 1.4 wt% , 0.6 to 1.3 wt%, 0.6 to 1.2 wt%, 0.6 to 1 wt%, 0.7 to 1.4 wt%, 0.7 to 1.3 wt%, 0.7 to 1.2 wt%, or 0.7 to 1 wt%.

Such polyarylene sulfide blended resin monofilament fibers include a polyarylene sulfide blended resin whose melt viscosity is greatly increased compared to both the first polyarylene sulfide resin and the second polyarylene sulfide resin, and thus has remarkable processability and abrasion resistance. It can show excellent effect. Although not wishing to be bound by a particular theory, when the melt viscosity increases, the frequency of single yarn shredding due to extrusion and drawing during monofilament fiber processing is significantly reduced, and processability can be improved. In addition, the uniformity of the thickness and surface of the fiber (ie, the uniformity of the fiber) can be secured, and abrasion resistance can also be improved. Furthermore, these polyarylene sulfide mixed resin monofilament fibers can exhibit an effect of further improving physical properties such as tensile strength and tensile elongation.

[Post-processed polyarylene sulfide blended resin monofilament fibers]

According to an embodiment, a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized into a first polyarylene sulfide resin in which a terminal group derived from a compatibilizing agent is introduced, and then processed first polyarylene sulfide resin, and A post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound, wherein the post-processed polyarylene sulfide mixed resin comprises the first polyarylene sulfide resin. A monofilament fiber (hereinafter, post-processed polyarylene sulfide monofilament fiber) having an increased melt viscosity compared to the arithmetic mean of the melt viscosity of the sulfide resin and the melt viscosity of the second polyarylene sulfide resin.

According to another embodiment, a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized into a first polyarylene sulfide resin in which a terminal group derived from a compatibilizing agent is introduced, and then processed first polyarylene sulfide resin, and a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized, wherein the melt viscosity of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin are calculated. preparing a composition comprising a post-processed polyarylene sulfide blended resin having an increased melt viscosity compared to the average; and spinning and/or drawing the composition. A method for producing monofilament fibers is provided.

In some embodiments, the stretching may be performed at a stretching ratio of 2.5 to 5.5 times. For example, fibers spun from the composition containing the post-processed polyarylene sulfide mixed resin may be stretched 2.5 to 5.5 times. In this case, the stretching strength of monofilament fibers can be improved. For example, the tensile strength of the post-processed monofilament fiber drawn at the draw ratio may be 3.0 g/de` or more, preferably 3.2 g/de` or more, 3.3 g/de` or more, or 3.6 g/de`. or more, 3.7 g/de` or more, or 3.8 g/de` or more.

Post-processed first polyarylene sulfide resin

The post-processed first polyarylene sulfide resin may be prepared by post-processing the first polyarylene sulfide resin using a compatibilizer. In addition, the post-processed first polyarylene sulfide resin may include a first polyarylene sulfide resin; and a terminal group derived from a compatibilizer.

The first polyarylene sulfide resin is as described above.

The compatibilizer for post-processing the first polyarylene sulfide resin may be a compound including a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group. Specifically, the compatibilizer may be one or more of the compounds represented by one of Formulas 5 to 8 below.

[Formula 5]

Y ¹ and Y ² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ , and B ¹ to B ⁷ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted phenyl group, and Z ¹ 'to Z ⁴ ' is each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms, p ¹ and p ² are each independently an integer of 1 to 3, provided that At least one of Y ¹ and Y ² is selected from the group consisting of -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ .

When Z ¹ 'and Z ² ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be linked to each other to form a benzene ring, and Z ³ 'and Z ⁴ ' may have 2 carbon atoms When it is an alkylene group and is bonded to two adjacent carbon atoms, it can be connected to each other to form a benzene ring.

When p ¹ or p ² is 2 or more, 2 or more Y ¹ or Y ² bonded to one aromatic ring may be identical to or different from each other. Also, Z ¹ 'and Z ³ ' may be the same as or different from each other, and Z ² 'and Z ⁴ ' may be the same as or different from each other.

The substituted alkyl group having 1 or 2 carbon atoms or the substituted alkenyl group having 1 or 2 carbon atoms of Z ¹ 'to Z ⁴ ' may have a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group.

An alkyl group having 1 to 3 carbon atoms or a substituted phenyl group in which one of B ¹ to B ⁷ is substituted may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.

Z ¹ ′ and Z ² ′ may be bonded to two adjacent carbon atoms, and Z ³ ′ and Z ⁴ ′ may be bonded to two adjacent carbon atoms. In addition, at least one or two or more of Z ¹ 'to Z ⁴ ' may not be a hydrogen group.

[Formula 6]

Y ³ to Y ⁶ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ , and B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R ¹ 'to R ⁴ 'are independently selected from the group consisting of an alkyl group having 1 to 5 carbon atoms. It is selected from the group consisting of an alkylene group and an alkoxy group, provided that at least one of Y ³ to Y ⁶ is -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ selected from the group consisting of Here, at least one of Y ³ to Y ⁶ may be -SB ⁹ in which B ⁹ is a hydrogen group.

[Formula 7]

Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ , and B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, and R ⁵ 'and R ⁶ ' are each independently a carbon atom number of 1 to 5 is an alkylene group.

[Formula 8]

Y ¹³ may be selected from the group consisting of a halo group, -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ , and B ²² to B ²⁸ are each independently It is selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group, W' is a halo group, and Z ⁵ 'and Z ⁶ ' are Each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms, and q is an integer of 1 to 3.

When Z ⁵ 'and Z ⁶ ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring. When q is 2 or more, 2 or more Y ¹³ bonded to one aromatic ring may be the same as or different from each other.

Z ⁵ 'and Z ⁶ ' may be bonded to two neighboring carbon atoms. Also, at least one of Z ⁵ 'and Z ⁶ ' may not be a hydrogen group. In addition, at least one of Y ¹³ may be selected from the group consisting of -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ .

The substituted alkyl group having 1 or 2 carbon atoms or the substituted phenyl group of B ²² to B ²⁸ may have a substituent of the alkyl group having 1 or 2 carbon atoms or the phenyl group.

In addition, compatibilizers include dithiobisdibenzoic acid, dithiodianiline, bis(hydroxyphenyl) disulfide, (triethoxysilyl)propanethiol, bis((triethoxysilyl)propyl)disulfane and iodophenyl ethyl ether. It may be at least one selected from the group consisting of, but is not particularly limited thereto. More specifically, the compatibilizer is 2,2'-dithiobisdibenzoic acid, 4,4'-dithiodianiline, bis(3-hydroxyphenyl) disulfide, bis(4-hydroxyphenyl) disulfide, 3-(tri It may be at least one selected from the group consisting of ethoxysilyl)propane-1-thiol, 1,2-bis(3-(triethoxysilyl)propyl)disulfane and 4-iodophenyl ethyl ether, but is particularly limited thereto It doesn't work.

The compatibilizing agent may cause a substitution reaction with an iodine atom that may be located at an end of the first polyarylene sulfide resin, or may perform the role of the compatibilizing agent itself without reaction. When the first polyarylene sulfide resin is post-processed with a compatibilizer, the main chain and/or terminal atmosphere of the first polyarylene sulfide resin can be changed from hydrophobic to hydrophilic, and through this, other resins having hydrophilic functional groups and/or reactive groups. , compatibility with inorganic fillers, etc. can be improved. Accordingly, the mechanical strength of the final product using the post-processed first polyarylene sulfide resin can be improved and the amount of outgas generated by heating can be significantly reduced.

The compatibilizing agent may react with the first polyarylene sulfide resin to impart terminal groups to the first polyarylene sulfide resin. Accordingly, the post-processed first polyarylene sulfide resin may have terminal groups derived from the compatibilizer.

The terminal group derived from the compatibilizer may mean a functional group possessed by the compatibilizer. Specifically, the compatibilizer may be a compound containing a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, a sulfonate group, and the like. group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.

More specifically, the terminal group derived from the compatibilizer may have a structure represented by one of Formulas 9 to 12 below.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In the above formula, Z ¹ ', Z ² ', Z ⁵ ', Z ⁶ ', Y ¹ , Y ³ to Y ⁵ , Y ⁷ to Y ⁹ , Y ¹³ , R ¹ ' to R ⁵ ', p ¹ and q are As described above.

The compatibilizer may be included in an amount of 0.001 to 10% by weight, 0.001 to 5% by weight, 0.01 to 3% by weight, or 0.1 to 2% by weight based on the total weight of the first polyarylene sulfide resin. When the first polyarylene sulfide resin is post-processed using a compatibilizer after polymerization, the reaction efficiency of the compatibilizer is remarkably superior compared to the case where the same compound is added as a polymerization inhibitor during polymerization of the resin, so that remaining in the final resin It is possible to maximize the content of the functional group, and also achieve the target content of the functional group to be introduced into the final resin through the compatibilizer while using a small amount of the compatibilizer. When the same compound is added as a polymerization inhibitor, the reaction efficiency is low because the compound is decomposed by a high-temperature environment for a long time required for the polymerization reaction or is discharged during the reaction. Therefore, when the first polyarylene sulfide resin is post-processed with a compatibilizing agent, decomposition can be minimized due to a short residence time in a high-temperature environment, and due to the characteristics of the post-processing process of applying a vacuum, it can cause outgas. The addition amount of polymerization inhibitor/compatibility agent can be lowered, and by-products caused by side reactions can be minimized to reduce outgassing amount and improve compatibility at the same time. In addition, since the first polyarylene sulfide resin post-processed with the compatibilizer can exhibit a low single yarn rate by reducing the number of defects in the spinning process as the amount of outgas is reduced as described above, the productivity per unit time is high and the production cycle can have a reducing effect.

Post-processing using compatibilizers can be performed by hot mixing. Hot mixing may be performed at a temperature of 290 to 330 °C. In addition, it can be carried out in a non-oxidizing atmosphere or vacuum conditions to achieve a high degree of polymerization while preventing oxidative crosslinking. In a non-oxidizing atmosphere, the oxygen concentration of the gas phase may be less than 5% by volume or less than 2% by volume, and more specifically, the gas phase may be substantially free of oxygen. When post-processing is performed through high-temperature mixing, since iodine, which may be partially present at the end of the first polyarylene sulfide resin, is sufficiently removed and the shrinkage rate is reduced due to excellent crystallinity, using the post-processed first polyarylene sulfide The dimensional stability of the final article produced may be improved.

In addition, high-temperature mixing may be performed in a reactor capable of heating and stirring. For example, the reactor may be made of various materials such as SUS. High-temperature mixing may be performed in a twin screw extruder, and the diameter ratio (L/D) of the twin screw extruder may be about 30 to 50. For example, the first polyarylene sulfide resin may be introduced through the main inlet of the twin-screw extruder, and the first polyarylene sulfide resin may be mixed with other additives and compatibilizers added in small amounts before being introduced into the main inlet. .

Post-processed polyarylene sulfide blended resin monofilament fibers

The post-processed polyarylene sulfide blended resin monofilament fiber includes a post-processed polyarylene sulfide blended resin composed of a first polyarylene sulfide resin and a second polyarylene sulfide resin; and optionally a heat stabilizer.

However, the post-processing of the first polyarylene sulfide resin may be performed before mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin, may be performed together with mixing, or may be performed after mixing. there is. In addition, it may be performed before mixing and may be further performed together with mixing or may be performed after mixing, and other combinations are possible without limitation. For example, the post-processing of the first polyarylene sulfide resin is performed by introducing a compatibilizer into the twin screw extruder when melt mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin into the twin screw extruder. can More specifically, it may be performed at a temperature of 280 to 330 °C, preferably 290 to 310 °C. At this time, the discharge amount of the resin component may be 5 to 600 kg / hr at a rotation speed of 100 to 450 rpm, and may be adjusted to 100 to 250 kg / hr in consideration of dispersibility. During the mixing, a polyarylene sulfide mixed resin having a further reduced amount of outgas may be prepared by degassing in a mixer or reactor equipped with a vacuum line.

An end of the post-processed polyarylene sulfide mixed resin may include a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group.

The post-processed polyarylene sulfide blended resin monofilament fibers contain 3 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, based on the total weight of the monofilament fibers. It may contain 80% by weight or more, 90% by weight or more, 95% by weight or more or 97% by weight or more.

In addition, the post-processed polyarylene sulfide blended resin monofilament fibers may include 3% by weight or less or 0.01 to 3% by weight of a heat stabilizer based on the total weight of the monofilament fibers, specifically, 0.01% by weight or more or It may contain 0.05% by weight or more, or 2% by weight or less, 1% by weight or less, or 0.5% by weight or less.

Meanwhile, the post-processed polyarylene sulfide mixed resin is composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin, which have been processed after being described above. The post-processed polyarylene sulfide mixed resin may have an increased melt viscosity compared to an arithmetic mean of melt viscosities of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin.

Specifically, the post-processed polyarylene sulfide mixed resin is the arithmetic mean of the melt viscosity (η _m ) and the melt viscosity (η _s ) of the first polyarylene sulfide resin included therein ((η _m + η _s )/2) of 105 to 400% melt viscosity. More specifically, the melt viscosity of the post-processed polyarylene sulfide mixed resin is 105 to 350%, 105 to 330%, 105 to 320%, 105 to 310%, 120 to 400%, 120 to 350%, and 120% on the same basis. to 330%, 120 to 320%, 120 to 310%, 140 to 400%, 140 to 350%, 140 to 330%, 140 to 320%, 140 to 310%, 170 to 400%, 170 to 350%, 170 to 330%, 170 to 320%, 170 to 310%, 210 to 400%, 210 to 350%, 210 to 330%, 210 to 320%, 210 to 310%, 220 to 400%, 220 to 350%, 220 to 330%, 220 to 320%, 220 to 310%, 270 to 400%, 270 to 350%, 270 to 330%, 270 to 320% or 270 to 310%.

In addition, the post-processed polyarylene sulfide mixed resin has a melt viscosity of 5,500 to 8,000 Pa s, 5,500 to 7,900 Pa s, 6,000 to 8,000 Pa s, 6,000 to 7,900 Pa s, 6,500 to 8,000 Pa s, 6,500 to 7,900 Pa s, 6,800 to 8,000 Pa s, 6,800 to 7,900 Pa s, 7,000 to 8,000 Pa s, 7,000 to 7,900 Pa s, 7,300 to 8,000 Pa s or 7,300 to 7,300 Pa s there is.

The increase in melt viscosity may be achieved by a reaction between a disulfide bond of the post-processed first polyarylene sulfide resin and a terminal halogen of the second polyarylene sulfide resin, although not bound by a particular theory. In addition, the first polyarylene sulfide resin may have an end group derived from a compatibilizing agent, so that the interaction between the polyarylene sulfide resins is strengthened and the melt viscosity of the first polyarylene sulfide resin is further increased.

The post-processed polyarylene sulfide mixed resin may include 1 to 99.9% by weight of the post-processed first polyarylene sulfide resin based on the total weight of the post-processed polyarylene sulfide mixed resin, and more specifically, 10 to 99.9% by weight. 90 wt%, 10 to 80 wt%, 10 to 70 wt%, 10 to 60 wt%, 20 to 90 wt%, 20 to 80 wt%, 20 to 70 wt%, 20 to 60 wt%, 30 to 90 wt% %, 30 to 80% by weight, 30 to 70% by weight, 30 to 60% by weight, 35 to 90% by weight, 35 to 80% by weight, 35 to 70% by weight or 35 to 60% by weight.

In addition, the post-processed polyarylene sulfide mixed resin may include 1 to 99.9% by weight of the second polyarylene sulfide resin based on the total weight of the post-processed polyarylene sulfide mixed resin, and more specifically, 10 to 99.9% by weight. 90 wt%, 10 to 80 wt%, 10 to 70 wt%, 10 to 60 wt%, 20 to 90 wt%, 20 to 80 wt%, 20 to 70 wt%, 20 to 60 wt%, 30 to 90 wt% %, 30 to 80% by weight, 30 to 70% by weight, 30 to 60% by weight, 40 to 90% by weight, 40 to 80% by weight, 40 to 70% by weight or 40 to 60% by weight.

Alternatively, the post-processed polyarylene sulfide mixed resin may contain the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin in a ratio of 0.5:9.5 to 9.5:0.5, 1:9 to 9:1, 1:9 to 8:2, 1:9 to 7:3, 1:9 to 6:4, 2:8 to 9:1, 2:8 to 8:2, 2:8 to 7:3, 2:8 to 6: It may be included in a weight ratio of 4, 3:7 to 9:1, 3:7 to 8:2, 3:7 to 7:3 or 3:7 to 6:4.

Meanwhile, the melting point of the post-processed polyarylene sulfide mixed resin in which the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed is the same as described above for the post-processed first polyarylene sulfide resin.

In some embodiments, the post-processed polyarylene sulfide mixed resin may include 0.8% by weight or less of disulfide bonds based on the total weight. In this case, the post-processed polyarylene sulfide mixed resin may have improved processability and good cavity balance. Preferably, the disulfide bond may be included in an amount of 0.7% by weight or less, 0.1% by weight or more, 0.3% by weight or more, or 0.5% by weight or more.

The nonlinear index of the post-processed polyarylene sulfide mixed resin was 0.12 to 0.33, 0.12 to 0.30, 0.12 to 0.25, 0.12 to 0.20, 0.12 to 0.18, 0.13 to 0.33, 0.13 to 0.30, 0.13 to 0.25, 0.13 to 0.13, 0.18, 0.15 to 0.33, 0.15 to 0.30, 0.15 to 0.25, 0.15 to 0.20 or 0.15 to 0.18.

The weight average molecular weight of the post-processed polyarylene sulfide mixed resin is 25,000 g/mol or more, 30,000 g/mol or more, 35,000 g/mol or more, 40,000 g/mol or more, 43,000 g/mol or more, or 45,000 g/mol or more 100,000 g/mol or less, 80,000 g/mol or less, or 65,000 g/mol or less. Also, the number average molecular weight may be greater than or equal to 1,000 g/mol, greater than or equal to 5,000 g/mol, greater than or equal to 7,500 g/mol, greater than or equal to 9,000 g/mol, or greater than or equal to 10,000 g/mol, and less than or equal to 30,000 g/mol or greater than or equal to 25,000 g/mol. or less, 20,000 g/mol or less, 18,000 g/mol or less, or 16,500 g/mol or less. If the number average molecular weight is lower than the above range, the melt strength is insufficient and single yarns are easily generated in the spinning and / or drawing process, and when the number average molecular weight is higher than the above range, the die-well phenomenon is severe in the spinneret, so that kneading occurs and the spinning process becomes poor. can Also, the peak apex molecular weight can be greater than or equal to 10,000 g/mol, greater than or equal to 15,000 g/mol, greater than or equal to 20,000 g/mol, greater than or equal to 25,000 g/mol, or greater than or equal to 30,000 g/mol, and less than or equal to 140,000 g/mol, or greater than or equal to 100,000 g/mol. or less, 75,000 g/mol or less, or 70,000 g/mol or less.

The post-processed polyarylene sulfide mixed resin may have a polydispersity index (PDI) of 2.0 to 6.0, for example, 2.5 or more, 3.0 or more, 3.5 or more, or 4.0 or more, or 5.5 or less, 5.0 or less, or 4.6 or less.

The post-processed polyarylene sulfide mixed resin may include iodine derived from a diiodo aromatic compound, and the content of iodine is 1 to 10,000 ppm based on the total weight of the post-processed first polyarylene sulfide resin, specifically , 5 ppm or more, 10 ppm or more, 50 ppm or more, 100 ppm or more, 300 ppm or more, 500 ppm or more, or 600 ppm or more, 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less , 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, 2,000 ppm or less, 1,700 ppm or less, 1,400 ppm or less, 1,000 ppm or less, or 900 ppm or less, 1,000 ppm or less, 800 ppm or less, or 600 ppm or less.

The post-processed polyarylene sulfide blended resin may contain chlorine derived from raw materials used in the manufacture of the second polyarylene sulfide resin, and the chlorine content is based on the total weight of the post-processed polyarylene sulfide blended resin. It may be less than 1,300 ppm, less than 1,000 ppm, or less than 800 ppm, and may be more than 10 ppm, more than 50 ppm, more than 100 ppm, more than 150 ppm, more than 200 ppm, more than 300 ppm, or more than 400 ppm.

The post-processed polyarylene sulfide blend resin may include inorganic materials such as Fe, Na, Ca, and Li, and the content of such (metallic) inorganic materials is 200 ppm or less based on the total weight of the post-processed polyarylene sulfide blend resin. , 190 ppm or less or 160 ppm or less, and may be 10 ppm or more, 30 ppm or more, 50 ppm or more, 60 ppm or more, or 80 ppm or more.

In addition, the post-processed polyarylene sulfide mixed resin may have an oligomer content of 0.01 to 5% by weight based on the total weight of the post-processed polyarylene sulfide mixed resin, specifically, 0.10% by weight or more, 0.50% by weight or more. Or it may be 0.80 wt% or more, 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.30 wt% or less, 1.20 wt% or less, or 1.10 wt% or less.

The post-processed polyarylene sulfide mixed resin may have a branching index (α) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and 1.00 or less, 0.90 or less, 0.80 or less, 0.77 or less, or 0.75 or less. there is.

The post-processed polyarylene sulfide mixed resin has a crystallization temperature of 150 to 300 ° C, 150 to 250 ° C, 150 to 240 ° C, 150 to 230 ° C, 150 to 220 ° C, 200 to 300 ° C, 200 to 250 ° C, 200 to 240 ° C. °C, 200 to 230 °C, 200 to 220 °C, 210 to 300 °C, 210 to 250 °C, 210 to 240 °C, 210 to 230 °C or 210 to 220 °C.

The outgas amount of the post-processed polyarylene sulfide mixed resin may be 0.001 to 5% by weight, specifically, 0.3 to 1.4% by weight, 0.3 to 1.3% by weight, 0.3 to 1.2% by weight, 0.3 to 1% by weight, 0.3% by weight to 0.9 wt%, 0.4 to 1.4 wt%, 0.4 to 1.3 wt%, 0.4 to 1.2 wt%, 0.4 to 1 wt%, 0.4 to 0.9 wt%, 0.5 to 1.4 wt%, 0.5 to 1.3 wt%, 0.5 to 1.2 wt% 0.5 to 1%, 0.5 to 0.9%, 0.6 to 1.4%, 0.6 to 1.3%, 0.6 to 1.2%, 0.6 to 1% or 0.6 to 0.9%.

The post-processed polyarylene sulfide blended resin monofilament fiber includes a post-processed polyarylene sulfide blended resin whose melt viscosity is greatly increased compared to both the first polyarylene sulfide resin and the second polyarylene sulfide resin, Abrasion resistance can exhibit remarkably excellent effects. In particular, as the post-processed first polyarylene sulfide resin is included, the melt viscosity may be increased to a greater extent. Furthermore, the post-processed polyarylene sulfide mixed resin monofilament fiber can exhibit an effect of further improving physical properties such as tensile strength and tensile elongation.

[Production Example]

1. First polyarylene sulfide resin

Preparation Example a: Preparation of PPS a

A thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of filling nitrogen and applying vacuum were attached to a 5 L reactor, and 5,240 g of paradiiodobenzene and 450 g of elemental sulfur were introduced into the reactor. After completely melting and mixing the composition in the reactor containing paradiiodobenzene and elemental sulfur by heating to 180 ° C., starting from the initial reaction conditions of a temperature of 220 ° C. and a pressure of 350 torr, gradually increasing the temperature and reducing the pressure to a temperature of 300 ° C. And the polymerization reaction proceeded under the final reaction condition of a pressure of 1 torr or less. When a sample of the polymerization reaction product was taken and the molecular weight of the sample was measured by gel permeation chromatography, when the weight average molecular weight (Mw) of the polymerization reaction product reached about 15,000 g/mol, diphenyl as a polymerization inhibitor was added to the reactor. After adding 24 g of disulfide (Sigma-Aldrich-169021) and reacting for 1 hour, the pressure was gradually reduced to 0.5 torr or less, the reaction was further progressed for 1 hour, and then the reaction was completed. PPS a was prepared as a first polyarylene sulfide resin by processing into a pellet form using a cutter.

2. Second polyarylene sulfide resin

Preparation Example b1: Preparation of PPS b1

3,027 g of sodium sulfide pentahydrate and 5,400 g of NMP as a polar organic solvent were introduced into the reactor, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Next, a solution obtained by dissolving 2,646 g of paradichlorobenzene and 17.01 g of parachlorobenzoic acid in 2,070 g of NMP was introduced into the reactor, and polymerization was performed at 220 to 240° C. for 8 to 12 hours under a nitrogen atmosphere. After cooling the reactor, the polymerization reaction product was taken out and filtered. The filtered cake was further washed with 2,880 g of NMP, and after adding 10 L of ion-exchanged water to the cake containing NMP, it was stirred in an autoclave at 200° C. for 10 minutes, and then further filtered. The final filtered cake was dried at 130° C. for 3 hours to prepare PPS b1 as the second polyarylene sulfide resin.

Preparation Example b2: Preparation of PPS b2

3,027 g of sodium sulfide pentahydrate, 763 g of lithium chloride, and 5,400 g of NMP as a polar organic solvent were introduced into the reactor, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Next, a solution obtained by dissolving 2,646 g of paradichlorobenzene and 17.01 g of parachlorobenzoic acid in 2,070 g of NMP was introduced into the reactor, and polymerization was performed at 220 to 240° C. for 8 to 12 hours under a nitrogen atmosphere. After cooling the reactor, the polymerization reaction product was taken out and filtered. The filtered cake was further washed with 2,880 g of NMP, and after adding 10 L of ion-exchanged water to the cake containing NMP, it was stirred in an autoclave at 200° C. for 10 minutes, and then further filtered. The final filtered cake was dried at 130° C. for 3 hours to prepare PPS b2 as the second polyarylene sulfide resin.

3. Post-Processed First Polyarylene Sulfide Resin

Preparation Example c1: Preparation of PPS c1

99.7 parts by weight (1,496 g) of the first polyarylene sulfide resin (PPS a) prepared according to Preparation Example a and 0.3 parts by weight of 2,2'-dithiodibenzoic acid (Sigma-Aldrich-43761, purity 95.0% or more) as a compatibilizer Part (4.5 g) was put into a twin-screw kneading extruder, and then melt blending was performed at a temperature of 300° C. and a pressure of 500 mmHg or less. The melt-blended polyarylene sulfide resin was processed into a pellet form using a small strand cutter to prepare PPS c1 as a post-processed first polyarylene sulfide resin.

Preparation Example c2: Preparation of PPS c2

Except for using 0.3 parts by weight of 4,4'-dithiodianiline (Sigma-Aldrich-369462, purity of 98% or higher) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, the same procedure as in Preparation Example c1 was performed. , PPS c2 was prepared as a post-processed first polyarylene sulfide resin.

Preparation Example c3: Preparation of PPS c3

Except for using 0.3 parts by weight of bis(3-hydroxyphenyl) disulfide (TCI (Tokyo Chemical)-B3149, purity 97.0% or more (GC)) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, manufacture In the same manner as in Example c1, PPS c3 was prepared as a post-processed first polyarylene sulfide resin.

Preparation Example c4: Preparation of PPS c4

Preparation Example c1, except for using 0.3 parts by weight of 3-(triethoxysilyl)propane-1-thiol (Power chemical (Chinese company) SiSiB-PC2310) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer. In the same manner as in, PPS c4 was prepared as a post-processed first polyarylene sulfide resin.

Preparation Example c5: Preparation of PPS c5

As a compatibilizer, 0.3 parts by weight of 1,2-bis(3-(triethoxysilyl)propyl) disulfane (Power chemical (Chinese manufacturer) SiSiB-PC2200) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid. Other than that, PPS c5 was prepared as a post-processed first polyarylene sulfide resin in the same manner as in Preparation Example c1.

Preparation Example c6: Preparation of PPS c6

A post-processed first poly PPS c6 was prepared as an arylene sulfide resin.

4. Polyarylene sulfide resin monofilament fibers

The first polyarylene sulfide resin, the second polyarylene sulfide resin, and/or the post-processed first polyarylene sulfide resin prepared according to the above-described preparation example were mixed in a twin screw kneading extruder ( Toshiba Kikai Co., Ltd., TEM-35B) was melt-kneaded at 300 ° C. and processed into a pellet form using a small strand cutter to prepare a polyarylene sulfide mixed resin or a post-processed polyarylene sulfide mixed resin. .

Thereafter, each prepared resin and a heat stabilizer (Hindered phenol-based heat stabilizer, AO-60, manufactured by Adeka) were uniformly mixed together using a tumbler in a weight ratio shown in Tables 1 to 3 below, and a single-axis / double-axis extruder type small The molten polymer is discharged through a spinneret using a spinneret, spun at a spinning speed of 150 m/min, and solidified into a monofilament fiber form while passing through a cooling water bath. The solidified fibers in the cooling water bath were drawn at a draw ratio of 2.5 to 5.5 using a drawing machine and heat-set at 230° C. using a non-contact heater to prepare monofilament fibers.

Specifically, PPS A as the first polyarylene sulfide resin monofilament fibers, PPS B1 and B2 as the second polyarylene sulfide resin monofilament fibers, and PPS C1 to C6 as the post-processed first polyarylene sulfide resin monofilament fibers , PPS D1 to D5 as polyarylene sulfide blended resin monofilament fibers and PPS E1 to E10 as post-processed polyarylene sulfide blended resin monofilament fibers.

division PPS A PPS B1 PPS B2 PPS C1 PPS C2 PPS C3 PPS C4 PPS C5 PPS C6 PPS a 99.9 - - - - - - - - PPS b1 99.9 - PPS b2 - 99.9 PPS c1 - - - 99.9 - - - - - PPS-c2 - - - - 99.9 - - - - PPS c3 - - - - - 99.9 - - - PPS c4 - - - - - - 99.9 - - PPS-c5 - - - - - - - 99.9 - PPS-c6 - - - - - - - - 99.9 heat stabilizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 total 100.0

division PPS D1 PPS D2 PPS D3 PPS D4 PPS D5 PPS a 79.9 59.9 39.9 19.9 39.9 PPS b1 - - - - 60 PPS b2 20 40 60 80 heat stabilizer 0.1 0.1 0.1 0.1 0.1 total 100.0

division PPS E1 PPS E2 PPS E3 PPS E4 PPS E5 PPS E6 PPS E7 PPS E8 PPS E9 PPS E10 PPS b1 - - - - - - - - - 40 PPS b2 40 40 40 40 40 40 20 60 80 - PPS c1 59.9 - - - - - 79.9 39.9 19.9 59.9 PPS-c2 - 59.9 - - - - - - - - PPS c3 - - 59.9 - - - - - - - PPS c4 - - - 59.9 - - - - - - PPS-c5 - - - - 59.9 - - - - - PPS-c6 - - - - - 59.9 - - - - heat stabilizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 total 100.0

[Experimental Example]

With respect to the polyarylene sulfide resin prepared according to the above Preparation Example, melting point, crystallization temperature, melt viscosity, nonlinear index, molecular weight, polydispersity index, branching index, melt viscosity increase rate after high temperature exposure, outgas amount, iodine content, chlorine content , Inorganic content and oligomer content were measured / derived, and processability, abrasion resistance, tensile strength and tensile elongation of monofilament fibers were measured / derived by the following methods, and are shown in Tables 4 to 6 below.

(1) melting point (Tm) and crystallization temperature (Tc)

TA instrument's Q20 model differential scanning calorimetry (DSC) was used to raise the temperature from 30 °C to 320 °C at a rate of 10 °C/min, cool down to 30 °C at a rate of 10 °C/min, and then at 30 °C again. The melting point and crystallization temperature were measured while heating at a rate of 10°C/min to 320°C and cooling at a rate of 10°C/min to 30°C.

(2) melt viscosity (MV) and nonlinear index

Melt viscosity is a rotating disk viscometer, when the viscosity is measured at each frequency range of 0.6 to 500 rad / s by the frequency sweep method at 300 ° C, the viscosity at each frequency condition of 1.84 rad / s has been defined

The nonlinear index was calculated through Equation 2 below.

[Equation 2]

Nonlinear index = 1 - (melt viscosity at a shear rate of 17.3 s ^-1 ) / (melt viscosity at a shear rate of 3.22 s ^-1 ).

(3) number average molecular weight (Mn), weight average molecular weight (Mw), peak apex molecular weight (Mp) and polydispersity index (PDI)

The number average molecular weight, weight average molecular weight, and peak peak molecular weight of the polyarylene sulfide resin were measured by gel permeation chromatography under the following measurement conditions, and the polydispersity index was calculated as the ratio of the weight average molecular weight to the number average molecular weight measured. In all molecular weight measurements, 6 types of monodisperse polystyrene were used for calibration.

[Gel permeation chromatography measurement conditions]

Device: Agilent PL-220

Column: Agilent, PLgel pore size 105Å + 104Å + 500Å + 50Å (4 columns)

Column temperature: 210°C

Solvent: 1-chloronaphthalene

Measurement method: Triple system detector (RI, viscometer, light scatter 15° and 90°)

(4) branch ratio (α)

The branching index was defined as an α value calculated by applying the viscosity measured from the triple system detector to the Mark-Howink equation of Equation 4 below. The Mark Howink equation is a relational expression between molecular weight and intrinsic viscosity of a polymer, and the branching index (α) represents the degree of branching of a polymer. That is, the closer α is to 1, the more linear the polymer, and the closer to 0, the more branched the polymer.

[Equation 4]

[η] = K Х M ^α

In the above formula, η is an intrinsic viscosity, M is a weight average molecular weight, and K is a constant.

(5) disulfide bond (-S-S-) fraction

The bonded fraction of disulfide was calculated through Equation 1 below.

[Equation 1]

Disulfide bond fraction (% by weight) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (theoretical weight of sulfur in polyarylene sulfide)

(6) Outgassing amount

A sample of a predetermined amount of polyarylene sulfide resin was heated at 330° C. for 20 minutes, and the amount of gas generated was quantified in weight percent using a gas chromatograph (GC) mass spectrometer.

(7) iodine and chlorine content

The iodine and chlorine contents of the polyarylene sulfide resin were measured by ion chromatograph (IC) using an IC (AQF) Thermo Scientific ICS-2500 (Mitsubishi AQF-100).

(8) Inorganic content

About 0.2 g of the polyarylene sulfide resin sample was heated and decomposed with 30 mL of a mixed acid (65% nitric acid/60% perchloric acid/98% sulfuric acid, volume ratio 1:1:1), diluted with ultrapure water, and metallic inorganics (Fe, Na) , Ca, Li, etc.) was measured by ICP-AES (Agilent's 5100 model).

(9) Oligomer content

Among all the peaks of the polyarylene sulfide resin appearing in the high-temperature gel-permeation chromatography, the ratio of the polymer having a molecular weight of 1,000 g/mol or less was calculated in weight% and evaluated as an oligomer content.

(10) Machinability

The processability was determined as follows by measuring the number of thread breakages for 5 hours in the monofilament spinning process.

◎: 0 times of rejection

○: 1 time of rejection

△: 2-3 occurrences of trimming

Х: 4 or more rejections

(11) Wear resistance

The abrasion resistance of the monofilament fibers was evaluated according to the evaluation method disclosed in US Patent No. 5,460,869. Specifically, a fatigue test was performed using a squirrel cage-type polishing machine in which 12 carbon steel rods were arranged at equal intervals on a bolt fixing disc with a diameter of about 14.2 cm rotating around a shaft. One end of the monofilament fiber was knotted and fixed to each rod, and the other end was connected to a 300 g weight and brought into contact with the rod, and the shaft was rotated at 100 rpm. The test was continued until the monofilament fibers broke, and the abrasion resistance of the monofilament fibers was evaluated by measuring the number of turns at break.

(12) Tensile strength and tensile elongation

Tensile strength and tensile elongation of the monofilament fibers in a stretched state were measured using Zwick's Z010 according to the ISO 527-2 method.

Polyarylene Sulfide Blended Resin Monofilament Fiber

As can be seen from the table above, the PPS D1 to D5 including the polyarylene sulfide mixed resin having increased melt viscosity compared to the first polyarylene sulfide resin and the second polyarylene polyasulfide resin, the first polyarylene sulfide resin Compared to PPS A containing only sulfide resin, it has excellent processability, wear resistance, tensile strength and tensile elongation, and is superior to PPS B1 and PPS B2 containing only second polyarylene sulfide resin, in processability, wear resistance and tensile strength. was able to confirm

In particular, PPS D1 to D4 containing the second polyarylene sulfide resin prepared by additionally using lithium chloride had a higher melt viscosity increase rate than PPS D5, and it was confirmed that processability, wear resistance and tensile strength were more excellent. .

Post-processed polyarylene sulfide blended resin monofilament fibers

division comparative example PPS A PPS B1 PPS B2 PPS C1 PPS C2 PPS C3 PPS C4 PPS C5 PPS C6 content ratio PPS a 99.9 - - - - - - - - PPS b1 - 99.9 - - - - - - - PPS b2 - - 99.9 - - - - - - PPS c1 - - - 99.9 - - - - - PPS-c2 - - - - 99.9 - - - - PPS c3 - - - - - 99.8 - - - PPS c4 - - - - - - 99.9 - - PPS-c5 - - - - - - - 99.9 - PPS-c6 - - - - - - - - 99.9 heat stabilizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 total 100 Suzy Disulfide bond fraction (% by weight) 1.73 N.D. N.D. 1.1 1.0 1.0 1.1 1.4 0.7 Outgassing amount (% by weight) 0.24 1.42 1.83 0.05 0.05 0.05 0.09 0.02 0.10 Melt Viscosity (Pa s) 3850 3550 3350 2200 2300 2180 1950 2290 2010 Melt Viscosity Increase (%) - - - - - - - - - nonlinear index 0.340 0.100 0.110 0.10 0.10 0.11 0.10 0.09 0.12 Mn (g/mol) 11000 12400 11400 12000 12000 12400 12500 12800 12200 Mw (g/mol) 42400 55400 55900 42400 44200 43200 43100 43400 42900 Mp (g/mol) 26900 62500 62300 28000 28000 27900 27600 27600 27600 PDI 3.85 4.47 4.90 3.53 3.68 3.48 3.45 3.39 3.52 α 0.47 0.70 0.70 0.61 0.60 0.61 0.61 0.63 0.60 Iodine content (ppm) 2800 N.D. N.D. 1860 1800 1950 2100 1780 1990 Chlorine content (ppm) N.D. 1500 1300 N.D. N.D. N.D. N.D. N.D. N.D. Mineral content (ppm) N.D. 240 240 N.D. N.D. N.D. N.D. N.D. N.D. Li content (ppm) N.D. N.D. 50 Oligomer content (% by weight) 1.1 0.9 1.0 1.1 0.9 1.0 0.8 1.3 1.1 melting point (℃) 280.1 279.4 279.4 280.3 280.4 280.0 280.8 281.8 281.2 Crystallization temperature (℃) 223.6 233.5 233.5 218.7 217.9 216.4 220.0 216.4 223.2 fiber machinability × × × × × × × × × wear resistance 2000 2500 2300 1500 1700 1800 2000 1800 1600 Tensile strength (g/de`) 1.8 2.6 2.4 2.6 2.2 2.4 2.3 2.2 2.4 Tensile Elongation (%) 22 35 35 28 26 31 29 30 31

As can be seen from the table above, PPS E1 to E10 including a post-processed polyarylene sulfide mixed resin having an increased melt viscosity compared to the first polyarylene sulfide resin and the second polyarylene polyasulfide resin, the first polyarylene sulfide resin Compared to PPS A containing an arylene sulfide resin and PPS C1 to C6 containing a post-processed first polyarylene sulfide resin, it has excellent processability, wear resistance, tensile strength and tensile elongation, and the second polyarylene sulfide resin It was confirmed that the processability, wear resistance and tensile strength were excellent compared to the containing PPS B.

In particular, PPS E1 to E9 including the second polyarylene sulfide resin prepared by additionally using lithium chloride have a higher melt viscosity increase rate than PPS E10, and are more excellent in processability, wear resistance, tensile strength and tensile elongation. I was able to confirm.

Claims (16)

A polyaryl composed of a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor, and a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound. Contains a rene sulfide mixed resin,
The monofilament fiber of claim 1 , wherein the polyarylene sulfide blended resin has an increased melt viscosity compared to an arithmetic average of the melt viscosities of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin.
According to claim 1,
Based on the total weight of the monofilament fibers,
97 to 99.99% by weight of the polyarylene sulfide mixed resin,
A monofilament fiber comprising 0.01 to 3% by weight of a heat stabilizer.
According to claim 1,
The polyarylene sulfide mixed resin comprises the first polyarylene sulfide resin and the second polyarylene sulfide resin in a weight ratio of 1:9 to 9:1, monofilament fiber.
According to claim 1,
The monofilament fiber, wherein the second polyarylene sulfide resin is prepared by further including lithium chloride (LiCl) in a solution polymerization reaction product of the dihalo aromatic compound and the second sulfur compound.
According to claim 1,
The polyarylene sulfide blend resin has a melt viscosity of 105 to 400% based on the arithmetic average of the melt viscosity of the first polyarylene sulfide blend resin and the melt viscosity of the second polyarylene sulfide blend resin, monofilament fiber.
According to claim 1,
The polyarylene sulfide mixed resin has a melt viscosity of 5,500 to 8,000 Pa s under the condition of measuring in an angular frequency range of 0.6 to 500 rad / s by a frequency sweep method using a rotating disk viscometer at a temperature of 300 ° C. , monofilament fibers.
According to claim 1,
A monofilament fiber having a tensile strength of 3.0 g/de` or more when stretched by 2.5 to 5.5 times.
A first polyarylene sulfide resin obtained by introducing a terminal group derived from a compatibilizer into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized, and then processed, and a dihalo aromatic compound and A post-processed polyarylene sulfide mixed resin composed of a second polyarylene sulfide resin in which a second sulfur compound is solution polymerized;
Wherein the post-processed polyarylene sulfide blend resin has an increased melt viscosity compared to the arithmetic mean of the melt viscosity of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide resin.
According to claim 8,
Based on the total weight of the monofilament fibers,
97 to 99.99% by weight of the post-processed polyarylene sulfide mixed resin,
A monofilament fiber comprising 0.01 to 3% by weight of a heat stabilizer.
According to claim 8,
The post-processed polyarylene sulfide mixed resin comprises the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin in a weight ratio of 1:9 to 9:1, monofilament fiber.
According to claim 8,
The monofilament fiber, wherein the second polyarylene sulfide resin is prepared by further including lithium chloride (LiCl) in a solution polymerization reaction product of the dihalo aromatic compound and the second sulfur compound.
According to claim 8,
The post-processed polyarylene sulfide mixed resin has a melt viscosity of 105 to 400% based on the arithmetic average of the melt viscosity of the first polyarylene sulfide resin and the melt viscosity of the second polyarylene sulfide mixed resin, monofilament fibers.
According to claim 8,
The post-processed polyarylene sulfide mixed resin has a melt viscosity of 5,500 to 8,000 Pa s under the condition of measuring in an angular frequency range of 0.6 to 500 rad / s by a frequency sweep method using a rotating disk viscometer at a temperature of 300 ° C. Having, a monofilament fiber.
According to claim 8,
The compatibilizing agent comprises at least one functional group selected from the group consisting of a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group, monofilament fibers.
According to claim 8,
The compatibilizing agent is a compound represented by one of the following formulas 5 to 8, monofilament fiber:
[Formula 5]

In the above formula,
Y ¹ and Y ² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ ,
B ¹ to B ⁷ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted phenyl group;
Z ¹ 'to Z ⁴ ' are each independently selected from the group consisting of a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms,
p ¹ and p ² are each independently an integer of 1 to 3;
When Z ¹ 'and Z ² ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
When Z ³ 'and Z ⁴ ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
The substituted alkyl group having 1 or 2 carbon atoms or the substituted alkenyl group having 1 or 2 carbon atoms of Z ¹ 'to Z ⁴ ' has a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group,
The B ¹ to B ⁷ substituted alkyl group having 1 to 3 carbon atoms or substituted phenyl group has a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group,
However, at least one of Y ¹ and Y ² is selected from the group consisting of -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ ;
[Formula 6]

In the above formula,
Y ³ to Y ⁶ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ ;
B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms;
R ¹ 'to R ⁴ 'are each independently selected from the group consisting of an alkylene group having 1 to 5 carbon atoms and an alkoxy group;
However, at least one of Y ³ to Y ⁶ is -SB ⁹ in which B ⁹ is a hydrogen group;
[Formula 7]

In the above formula,
Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ ;
B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms;
R ⁵ ' and R ⁶ ' are each independently an alkylene group having 1 to 5 carbon atoms;
[Formula 8]

In the above formula,
Y ¹³ is selected from the group consisting of halo, -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ ;
B ²² to B ²⁸ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group;
W' is halo;
Z ⁵ 'and Z ⁶ ' are each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms,
q is an integer from 1 to 3;
When Z ⁵ 'and Z ⁶ ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
The B ²² to B ²⁸ substituted alkyl group having 1 or 2 carbon atoms or the substituted phenyl group has a substituent of an alkyl group having 1 or 2 carbon atoms or a phenyl group,
However, at least one of Y ¹³ is selected from the group consisting of -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ .
According to claim 8,
A monofilament fiber having a tensile strength of 3.0 g/de` or more when stretched by 2.5 to 5.5 times.