KR20160139399A - Polyketone fishing line including polyketone fiber method for manufacturing the same - Google Patents

Abstract

The present invention relates to a fishing line made of polyketone fibers, and to a production method thereof. More specifically, the present invention relates to a fishing line exhibiting outstanding strength since the fishing line is made of polyketone fiber, and to a production method thereof.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fishing line comprising a polyketone fiber,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fishing line made of polyketone fibers and a method for manufacturing the same, and more particularly, to a fishing line made of polyketone fibers and having excellent strength and a method for producing the same.

Fishing rods made of high strength polyolefin fibers are known. Such fibers can be high strength polyethylene fibers, such as SPECTRA extended chain polyethylene fibers and yarns.

Typically, these high strength fibers are prepared by spinning a solution comprising a polyethylene gel swollen with a suitable solvent into an ultra high molecular weight polyethylene filament. The solvent is removed and the resulting yarn is stretched or drawn in one or more stages. Generally, these filaments are known as "gel spun" polyolefins, and gel-spun polyethylene is the most commercially available.

Fishing rods made of gel-spun polyethylene yarns are typically fabricated by braiding multifilament yarns. These fishing lines are advantageous over nylon monofilament ropes as well as other blended fishing line materials (such as polyester) because the ultra high molecular weight polyethylene strands have greater strength. However, many anglers prefer the feel of a monofilament fishing line, and the braid string can be torn off. In addition, the braided polyethylene strips need to be sheared with a shearing device, such as a scissors, rather than a commonly used compression type line clipper.

On the other hand, a polyketone having a structure in which repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are substantially alternately linked has excellent mechanical and thermal properties, and has high abrasion resistance, chemical resistance and gas barrier properties, Is expected to evolve. For example, polyketone is a useful material for resins, fibers and films with high strength and high heat resistance. Particularly, when a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more is used as a raw material, a fiber or a film having a very high strength and an elastic modulus can be obtained. Such fibers and films are expected to be widely used for building materials and industrial materials such as rubber reinforcements such as belts, hoses and tire cords, and concrete reinforcements.

The polyketone mainly comprising a repeating unit composed of ethylene and carbon monoxide has a high melting point of 200 DEG C or more, but under heat for a long time, heat denaturation such as three-dimensional crosslinking occurs, molding processability due to disappearance of fluidity is decreased, There is a problem that the mechanical and heat resistance performance of the molded article deteriorates. As a method of molding with high strength fibers or films, there is known a wet molding method in which a polyketone is dissolved in an aqueous solution of an inorganic salt such as zinc chloride (for example, a pamphlet of WO99 / 18143, a pamphlet of WO 00/09611 Etc). However, this method has problems such as heat denaturation of the polyketone by heating the polyketone-dissolved dopant for a long time, deterioration of the fluidity or radioactivity of the dopant, and deterioration of the mechanical properties of the resulting fiber and film.

Polyketone receives heat and causes chemical reaction such as formation of furan ring by Paal-Knorr reaction or generation of intramolecular and intermolecular crosslinking by aldol condensation, and deterioration by heat proceeds. This chemical reaction is greatly accelerated by the polymerization catalyst (palladium (Pd)) remaining in the polyketone. As a countermeasure against such deterioration by heat, a technique for reducing the amount of Pd remaining in the polyketone has been studied (for example, European Patent No. 285218, US Patent No. 4855400, and US Patent No. 4855401). Reduction of the amount of Pd remaining in the polyketone is effective in improving the heat resistance of the polyketone. However, the technology disclosed in these documents is a technique in which a polyketone obtained by a usual polymerization method is treated with a compound such as triphenylphosphine, triethylamine, or 1,3-bisdi (2-methoxyphenyl) This is a technique for performing the Pd extraction process for a long period of time, and it is not industrially applicable technology considering the cost of the cleaning equipment, cleaning and extraction solvent. Further, due to thermal degradation of the polyketone due to the long heat treatment, the amount of Pd is small, but the heat resistance of the obtained polyketone is not sufficient.

In the literature [Polymer, 42 (2001) 6283-6287], it has been found that polyketone polymerized in an acetone solvent is subjected to extraction treatment with 2,4-pentanedione to reduce the Pd content to 20 ppm or less to improve the heat resistance of the polyketone Lt; / RTI > This polyketone does not use alcohol as a polymerization solvent and therefore has very low polymerization activity under these conditions. In addition, a complicated Pd extraction treatment is required after polymerization and can not be industrially adopted from the viewpoints of productivity and cost. International Publication WO 00/09611 discloses a polyketone having a Pd content of 5 ppm. However, since the polyketone is obtained by polymerizing Pd at 80 and 5 MPa and removing Pd in the polymer by solvent extraction, there is a problem that the polymerization rate is very low and a long time heat treatment is required at the time of solvent extraction. In order to reduce the amount of Pd in the polyketone without performing the extraction treatment for a long time, it is necessary to produce a large amount of polyketone with a small amount of Pd, that is, to perform polymerization for a long time with high polymerization activity. As a polymerization method of high polymerization activity, several techniques have been known so far. For example, in Japanese Patent Laid-Open Nos. 1-201333, 2-115223, WO 00/68296, and WO 01/02463, it is preferable that 20 kg / g-Pd / hr < / RTI > at a very high polymerization activity. Here, the polymerization activity is an index (unit: kg / g-Pd / hr) in which the monomer shows the amount of the polymer produced per unit time by the catalyst (Pd in the present invention) It means that more polyketones are obtained from

However, all of the polyketones obtained by the polymerization process with high polymerization activity (20 kg / g-Pdhr or more) disclosed in these documents have low polymerization degree and an intrinsic viscosity of less than 2.5 dl / g, It was an insufficient polymerization technique.

On the other hand, regarding the terminal structure of the polyketone, the relationship between the kind of the polymerization solvent and the structure and ratio of the terminal end has been studied. Japanese Patent Application Laid-open No. 59-197427 discloses 1,3- Phenylphosphino) propane is used to describe the terminal structure and the ratio thereof when various polymerization solvents are used. For example, when an alcohol such as methanol or ethanol is used, an alkyl ester terminal and an alkyl ketone terminal are used. When a glycol such as ethylene glycol is used, a hydroxyalkyl terminal and an alkyl ketone terminal are used, and tetrahydrofuran, When an aprotic polar solvent is used, it is disclosed that only an alkyl ketone terminal is produced. In this document, it is described that when an alkyl ester end is produced, the equivalent ratio of the alkyl ester end (terminal group A) / alkyl ketone terminal (terminal group B) is not 1/1, but is in the range of 0.09 / 1 to 1.04 / 1 have. However, all of the polyketones exemplified in this document relate to polymers having a low molecular weight, and nothing has been disclosed for a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more. Specifically, in the examples of this document, the polyketone having terminal group A and terminal group B shown has a number average molecular weight of 250 to 7500. (Intrinsic viscosity 1.010-4 Mw0.85) described in the literature (for example, Japanese Unexamined Patent Publication (Kokai) No. 4-228613) was used as the molecular weight distribution (Mw / Mn) As a result of calculation of the viscosity, the intrinsic viscosity of the polyketone described in this Example was 0.03 to 0.54 dl / g, and it was not expected to exhibit high mechanical properties such as high strength and high elastic modulus. Further, the polyketone of this document has a very low polymerization activity, and the theoretical Pd content of the polyketone calculated from the product of the polymerization activity and the polymerization time (catalyst efficiency) is 100 ppm or more and contains a very large amount of Pd.

The polymerization conditions, the structure at the terminal end and the ratio thereof are studied for the terminal groups of the polyketone, but the relationship between the terminal structure and the characteristics of the polyketone is disclosed in, for example, Japanese Patent Application Laid- It is merely described that the characteristics of the polyketone do not depend on the terminal group structure. In particular, there is no disclosure of control of the end group structure as means for improving the thermal stability of the polyketone in the aqueous metal salt solution.

In addition, JP-A-10-0668572 describes a preferable structure and carbon number of the terminal group of polyketone. For example, when the terminal group is an alkyl ester group, the preferred alkyl group has 1 to 6 carbon atoms. When the number of carbon atoms is more than 7, it is difficult to polymerize the polyketone at a high polymerization activity, and in order to produce a polyketone having a small amount of Pd, a long time reaction is required and the productivity is lowered. The viscosity of the polymerization suspension is increased, And the recovery cost of the solvent is increased.

In order to solve the above problems, the present invention relates to a fishing line having excellent strength by manufacturing a fishing line using polyketone fibers and a method for manufacturing the fishing line.

In order to achieve the above-mentioned object, the present invention provides, in order to achieve the above-mentioned object, the present invention is a recording material comprising a repeating unit represented by the following general formulas (1) and (2) There is provided a fishing line comprising a polyketone fiber characterized in that a polyketone copolymer having an intrinsic viscosity of 5 to 7 dl / g is produced through a spinning process, a washing process, a drying process and a stretching process.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

The molecular weight distribution of the polyketone copolymer is preferably 1.5 to 4.0, and the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5, Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).

The polyketone fibers preferably have a fineness of 0.5 to 8.0 denier.

The drying step is preferably hot-rolled at 100 ° C to 230 ° C and preferably 1.0 to 2.0 times.

In addition, it is preferable that the stretching process is a method of passing through a heating chamber of 230 ° C to 300 ° C.

Further, the heat stabilizer is treated before the drying step and the stretching step.

In addition, the fishing line containing the polyketone fibers preferably has a strength of 15 g / d or more.

The present invention can provide a fishing line having excellent strength by manufacturing a fishing line using polyketone fibers.

1 is a view schematically showing the role of a heat-resistant stabilizer according to the prior art.
2 is a schematic view of a conventional hot air drying type dryer.
3 is a schematic view of a hot roll drying method according to the present invention.
Fig. 4 is a cross-sectional view of the dry irradiation according to the conventional hot air drying method.
Fig. 5 is a cross-section view of a dry-type drying method according to the present invention.

Hereinafter, the present invention will be described.

The present invention relates to a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), having a y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g, The present invention provides a fishing line including a polyketone fiber, which is manufactured through a process, a drying process and a stretching process.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

The molecular weight distribution of the polyketone copolymer is preferably 1.5 to 4.0, and the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5, Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).

In addition, it is characterized in that it is stretched 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step.

In addition, the drying step may be hot-rolled at 100 to 230 ° C, and the stretching step may be a heating chamber stretching method at 230 to 300 ° C.

In addition, it is preferable to treat the heat stabilizer before the drying step and the stretching step.

Hereinafter, the polymerization method of the polyketone used in the present invention will be described in detail.

One or more olefinically unsaturated compounds (simply referred to as " A "), wherein the monomer units are alternating, and thus the polymer is composed of units of the formula - (CO) -A'- wherein A 'represents the monomer units derived from the applied monomer A ) And a high molecular weight linear polymer of carbon monoxide can be prepared by contacting the monomer with a solution of the palladium-containing catalyst composition in a dilute solution in which the polymer does not dissolve or actually dissolve. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.

The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.

In the present invention, not only methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, but also mixed solvents comprising acetic acid and water, ethanol, propanol, and isopropanol can be used as the liquid medium. Particularly, when a mixed solvent of acetic acid and water is used as a liquid medium in the production of polyketone, the catalyst activity can be improved while reducing the production cost of polyketone. Further, since the use of methanol or a dichloromethane solvent forms a mechanism for causing a stopping reaction during the polymerization step, the use of acetic acid or water other than methanol or dichloromethane in the solvent does not have an effect of stopping the catalytic activity stochastically, It plays a big role in improvement.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the effect of the catalyst is less affected. When the concentration of water is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, It is most preferable to use palladium acetate.

Examples of ligands (b) having a Group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) Bis [di (2-methylphenyl) phosphino] propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine, ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) Bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) ) Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

The ligand (b) having a group 15 atom preferred in the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, is 1,3-bis- [di (2-methoxyphenyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and more preferably 1,3-bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- ) Phosphine) is better.

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

Particularly, the anion (c) of the acid having a pKa of 4 or less, which is preferred in the present invention, is p-toluenesulfonic acid. When used together with a mixed solvent of acetic acid and water as a liquid medium, not only has a high catalytic activity, It becomes possible to produce a polyketone having a suitable high intrinsic viscosity.

The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.

The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.

In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, - C2 to C20 alpha-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 5 mol% or more than 95 mol%, the reactivity is poor and the physical properties of the produced polyketone may be deteriorated.

On the other hand, the polyketone copolymer used as the fiber may be composed of ethylene, propylene and carbon monoxide. The larger the molar ratio of propylene is, the more unsuitable as a fishing line. The molar ratio of ethylene to propylene is preferably 100: 0 to 90:10 .

On the other hand, the molecular weight distribution of the polyketone is preferably in the range of 1.5 to 4.0, and if it is less than 1.5, the polymerization yield is lowered. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger. The molecular weight distribution of the most preferred polyketones is 2.5 to 3.5.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 to 300 占 폚, and is generally 210 to 270 占 폚. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, and preferably 5.0 dl / g to 7.0 dl / g . At this time, when the intrinsic viscosity of the polyketone polymer is less than 5.0, the mechanical strength is lowered in production of the fiber, and when it exceeds 7.0, the workability is lowered.

Further, the polyketone fishing line made of the polyketone is characterized by having a strength of 15 g / d or more.

The production method of the polyketone fiber of the present invention will be described.

First, the solution extruded from the spinning nozzle passes through an air gap in a vertical direction and solidifies in a coagulating bath. At this time, the air gap is radiated within a range of about 1 to 300 mm in order to obtain a dense and uniform fiber and to provide a smooth cooling effect.

Thereafter, the filament passing through the coagulation bath passes through the water bath. At this time, the temperature of the coagulation bath and water bath is maintained at about 0 to 80 ° C to prevent the deterioration of physical properties due to the formation of pores in the fiber structure due to rapid desolvation.

The fibers having passed through the water-washing tank were subjected to acid washing in an aqueous solution containing the acid, passed through a second water-washing bath to remove the acid, passed through a dryer, and then emulsified in an emulsion- do.

In addition, in order to improve the flatness and improve the property of the housing, it passed the interlace nozzle. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm 2, and the number of entanglement per filament was 2 to 40.

Thereafter, the filament yarn passed through the interlace nozzle is dried while passing through the drying device. In this case, the drying temperature and the drying method have a great influence on the post-processing and physical properties of the filament.

The filament that has passed through the drying device is finally wound in a winder through a secondary emulsion treatment device.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance. In the drawing method, hot air heating method and roller heating method are used, but since the filament is in contact with the roller surface in the roller heating method, the fiber surface is likely to be damaged, so that hot air heating method is more effective in manufacturing high strength polyketone fiber. However, the inventors of the present invention have found that by applying a heat-resistant stabilizer while applying a roller heating method, especially a hot-roll drying method, and performing a stretching process of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, High strength multifilament could be obtained. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

That is, the present invention is characterized in that the stretching process is performed by using a method of passing through a heating chamber at 230 ° C to 300 ° C.

On the other hand, as the solvent for dissolving the polyketone, it is preferable to use an aqueous solution containing at least one metal salt selected from the group consisting of zinc salts, calcium salts, lithium salts, thiocyanates and iron salts. Specific examples of the zinc salt include zinc bromide, zinc chloride and zinc iodide. Examples of the calcium salt include calcium bromide, calcium chloride and calcium iodide. Examples of the lithium salt include lithium bromide, lithium chloride, lithium iodide . Examples of the iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in terms of the solubility of the raw material polyketone and the homogeneity of the polyketone solution.

The concentration of the metal salt in the metal salt aqueous solution of the present invention is preferably 30 to 80% by weight. If the concentration of the metal salt is less than 30% by weight, the solubility decreases. If the concentration of the metal salt is more than 80% by weight, the cost for concentration increases, which is disadvantageous in terms of economy. As the solvent for dissolving the metal salt, water, methanol, ethanol and the like can be used. In particular, water is used in the present invention because it is economical and advantageous in solvent recovery.

In order to obtain a polyketone fiber having high strength and high fatigue resistance and dimensional stability as a core technical matter in the present invention, an aqueous solution containing zinc bromide is preferable, and the composition ratio of zinc bromide in the metal salt is an important factor. For example, in an aqueous solution containing only zinc bromide and calcium bromide, the weight ratio of zinc bromide to calcium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40. Further, in the aqueous solution containing zinc bromide, calcium bromide and lithium bromide, the total weight ratio of zinc bromide, calcium bromide and lithium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40, , The weight ratio of calcium bromide to lithium bromide is 40/60 to 90/10, preferably 60/40 to 85/15.

The production method of the polyketone solution is not particularly limited, but an example of a preferable production method will be described below.

The metal salt aqueous solution maintained at 20 to 40 캜 is defoamed at a pressure of 200 torr or less, the polyketone polymer is heated to 60 to 100 캜 under a vacuum of 200 torr or less, and stirred for 0.5 to 10 hours to prepare a sufficiently dissolved homogeneous dope .

In the present invention, the polyketone polymer may be mixed with other polymer materials or additives. Examples of the polymer material include polyvinyl alcohol, carboxymethyl polyketone, and polyethylene glycol. Examples of additives include viscosity improvers, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method for producing a polyketone fiber including spinning, washing, drying and stretching the homogeneous polyketone solution of the present invention will be described in more detail. However, the polyketone fibers claimed in the present invention are not limited by the following process.

The spinning process of the method according to the present invention will be described in more detail. The spinning stock solution is extruded and spun through a spinning nozzle to allow the fiber spinning solution to pass through the air layer to reach the coagulation bath, .

The shape of the spinning nozzle used is usually circular, and the nozzle diameter is 50 to 200 mm, more preferably 80 to 130 mm. When the nozzle diameter is less than 50 mm, the distance between the orifices is too short, so that the adhesion may occur before the discharged solution solidifies. If the nozzle diameter is too large, peripheral devices such as spinning packs and nozzles become large,

When the fiber stock solution passing through the spinning nozzle coagulates in the upper coagulating solution, the larger the diameter of the fluid becomes, the larger the difference in the coagulation speed between the surface and the inside becomes, and it becomes difficult to obtain a dense and uniform tissue fiber. Therefore, when the polyketone solution is spun, even if the same discharge amount is maintained, the spun fibers having a smaller diameter can be obtained in the coagulating solution while maintaining an appropriate air layer.

The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. It is difficult to increase the spinning speed because the too short air layer distance increases the micropore generation rate due to the rapid surface layer coagulation and desolvation process, and it is difficult to increase the spinning speed. On the other hand, the too long air layer distance is affected by the adhesion of the filament, It is difficult to maintain process stability.

The composition of the coagulating bath used in the present invention is such that the concentration of the metal salt aqueous solution is 1 to 20% by weight. The coagulating bath temperature is maintained at -10 to 60 ° C, more preferably -5 to 20 ° C. In the coagulation bath, when the filament passes through the coagulation bath of the multifilament, when the spinning speed is increased by 500 m / min or more, the coagulation of the coagulating solution becomes severe due to the friction between the filament and coagulating liquid. In order to improve the productivity by increasing the excellent physical properties and the spinning speed through the stretching orientation, such a phenomenon is a factor that hinders the process stability, so that it is necessary to minimize such a phenomenon.

In the present invention, the coagulating bath is characterized by a temperature of -10 to 40 ° C and a metal salt concentration of 1 to 30% by weight, and the water bath is preferably at a temperature of 0 to 40 ° C and a metal salt concentration of 1 to 30% The acid washing bath preferably has a temperature of 0 to 40 캜 and an acid concentration of 0.5 to 2% by weight, and the secondary washing bath for acid removal is maintained at a temperature of 30 to 70 캜.

Also, in the present invention, the temperature of the dryer is 100 ° C or higher, preferably 200 ° C or higher, and the emulsion, heat-resistant agent, antioxidant or stabilizer is added to the fiber passed through the dryer.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance.

Hereinafter, the stretching process and drying method important in the present invention will be described.

The present invention provides a high-strength fiber by securing the heat stability of the polyketone during wet spinning and by directly drying the fiber. In the conventional spinning process, the maximum strength is 13 g / d even at the time of germination drying and optimization of the stretching temperature. However, the present invention optimizes the heating method and the temperature profile of the drying method to form a dense structure by fusion- As a result, the draw ratio and the strength are improved. Further, in order to prevent thermal deterioration of the polyketone at the time of heating, the stretching magnification and strength are improved by a process including a heat stabilizer during drying and stretching.

Polyketone fibers have oxidation or degradation mechanisms at high temperatures. As a radical oxidation mechanism, polyketone releases carbon dioxide and oxidative degradation occurs when exposed to oxygen at temperatures above 90 ° C. In addition, due to the radical deterioration mechanism, when the polyketone is exposed to a high temperature of 200 ° C or more, carbon monoxide and ethylene are released and thermal degradation occurs. A heat-resistant stabilizer is used to prevent oxidation and deterioration of the polyketone at such a high temperature. As the heat-resistant stabilizer, both of antioxidants capable of preventing radical oxidation and deterioration can be used.

Preferably, phenolic heat stabilizers are used, and one or more heat stabilizers may be used alone or in combination. Oxidation and deterioration prevention mechanisms prevent radicals by radicals by capturing radicals with heat stabilizers (alkyl radicals) generated by heat or ultraviolet rays (see FIG. 1). The heat stabilizer may be used before drying or before stretching, and the immersion or application method may be used alone or in combination. Specifically, in an embodiment of the present invention, 0.1% of a solution of a phenolic heat stabilizer obtained by mixing a phenolic heat stabilizer with a methanol solvent in a pre-drying step and a stretching step is applied in a pre-drying step and a drawing step, Of the heat stabilizer was 250 ppm, but after the drying and the stretching step, 25 ppm remained. The heat stabilizer should be used in an appropriate amount depending on the process. If the heat stabilizer is large, the workability is poor. If the heat stabilizer is small, the heat stabilization effect is not sufficient. The heat stabilizer may be used in one-pot or two-pot or more.

Meanwhile, in order to increase the strength of the fiber, the present invention uses a direct drying method of a hot roller drying method, rather than an indirect drying method of a hot air drying method. In the conventional hot air drying method, a hot air drying method as shown in FIG. 2 was used at a temperature of 180 ° C. for a retention time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the affixation, but it is difficult to generate fusion, loops, static electricity, and fusion structure, so that the structure is not as dense (see FIG. 4). The present invention uses a hot-roll drying method as shown in Fig. 3 for a retention time of about 1 minute and 30 seconds at a temperature of 220 to 230 ° C. When such a drying method is used, there is no entanglement, less static electricity is generated, and a fine structure is formed due to the formation of a fusion structure, which is easy to apply for commercialization (see FIG. 5).

In addition, the present invention is subjected to a stretching process in which the fibers are stretched 15 to 18 times. For stretching the polyketone fibers, stretching is carried out in one or more stages. In the case of multi-stage stretching, it is preferable to perform the temperature-raising stretching in which the stretching temperature gradually increases with an increase in the stretching magnification. Specifically, the stretching process is performed at a temperature of 240 to 270 ° C, and the residence time is within about 1 minute and 30 seconds, and the first and second stages are performed. Stretching is carried out from step 1 to step 7, second step to step 2.5, and step 2 is stepwise stretching in a 3 step form. After the first stage, the elongation of the polyketone fibers is 10% and the strength is 8 g / d. After the second stage, the elongation is about 5.2%, and the strength of the polyketone fibers is 20 g / d.

In addition, since the polyketone is thermally deteriorated at a high temperature due to the drying and stretching processes described above, a heat stabilizer is added. It is applied before drying or before stretching. In the present invention, both raw or dip can be used. In general, when the two-dip or more is performed, the elongation of the fiber is decreased independently of the increase in the strength, but in the case of the hot-roll drying method according to the present invention, there is little decrease in elongation.

The fiber density of the monofilament is 1.295 to 1.310 g / cm < 3 > by the hot-roll drying method of the present invention and the step of adding the heat stabilizer, and the structure thereof is as shown in Fig.

The polyketone fibers produced by the present invention can be made into industrial products. Preferably, it may be applied to a fishing line, but the scope of the present invention is not limited thereto.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to specific examples and comparative examples. However, these examples are merely intended to clarify the present invention and are not intended to limit the scope of the present invention.

Example 1

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 30 캜 at an injection temperature of 25 캜 by a gear pump at a rate of 13000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C and operating the screw at 110 rpm.

At this time, a circular nozzle having a nozzle hole number and a hole diameter of 1 and 2 mm and an L / D of 1 was used, and an air gap was 10 mm. The concentration of the polyketone in the discharged solution was 8.2% by weight, and it was in a homogeneous state free of undissolved polyketone particles.

The fiber thus obtained is subjected to stretching at 1.2 times in the course of washing, and the heat stabilizer is dipped in a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer before drying. In the drying process, 1.2-fold stretching was performed by a hot-roll drying method, and then fibers were produced in a heating chamber method at a total stretching magnification of 16.8 times, stretched at a stretch ratio of 7 times at the first stretch, 2.4 times at the second stretch, 1.5, 1.3, and 1.23 times, and each step is performed at temperatures of 240, 255, 265, and 268 ° C.

A fishing line was prepared from the monofilaments obtained through the above process.

Example 2

A fishing line was prepared in the same manner as in Example 1, except that polyketone fibers were produced by performing 1.2-fold stretching in the washing process.

Example 3

A fishing line was prepared in the same manner as in Example 1, except that polyketone fibers were produced by performing 1.6-fold stretching in the washing process.

Comparative Example 1

The polyamide resin composition,? -Caprolactam and bisamide compound were dry mixed with a tumbling blender. The mixture was melt-spun with an extruder equipped with a gear pump at the end of a single-screw extruder equipped with a full flight screw having a cylinder diameter of 40 mm and a L / D of 27, cooled and solidified through a cooling water bath having a water temperature of 15 ° C Followed by wet heat stretching at 95 占 폚 and 100% RH at 3.2 times, followed by dry stretching at 1.5 times in dry air at 280 占 폚 and finally dry annealing at a relaxation rate of 0.95 times at 290 占 폚 or lower to obtain monofilaments having a diameter of 3 mm. A fishing line was prepared from the monofilaments obtained through the above process.

Experimental Example 1

The properties of the fishing rods produced in Examples 1 to 3 and Comparative Example 1 were evaluated, and the results are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Strength (g / d) 20.0 21.0 21.2 7.7 Shinto (%) 6.0 5.9 6.1 51

As can be seen from the above Table 1, it was found that the fishing line manufactured in Examples 1 to 3 had significantly higher strength and elongation than Comparative Example 1. [

Claims (7)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having an y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g is subjected to spinning, Characterized in that the polyketone fibers are manufactured through a process and a stretching process.
- [- CH2CH2-CO-] x- (1)
- [- CH2 --CH (CH3) - CO--] y- (2)
(x and y are mole% of each of the general formulas (1) and (2) in the polymer) The method according to claim 1,
Wherein the polyketone fibers have a strength of at least 15 g / d. The method according to claim 1,
Wherein the polyketone copolymer has a molecular weight distribution of 2.5 to 3.5. The method according to claim 1,
The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is a bis (methylene) bis (bis (2-methoxyphenyl) -1,3-dioxane-5,5- Wherein the polyketone fiber is a polypropylene fiber. The method according to claim 1,
Wherein the polyketone fiber is stretched 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step. The method according to claim 1,
Characterized in that the drying step is a hot-roll drying at 100 to 230 ° C and the stretching step is a heating chamber stretching at 230 to 300 ° C. The method according to claim 1,
Characterized in that the heat-resistant stabilizer is treated before the drying step and the stretching step.

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