KR20160045400A

KR20160045400A - Poly ketone tire cord for improving strength

Info

Publication number: KR20160045400A
Application number: KR1020140140875A
Authority: KR
Inventors: 최영민; 황순동; 이득진
Original assignee: 주식회사 효성
Priority date: 2014-10-17
Filing date: 2014-10-17
Publication date: 2016-04-27

Abstract

Provided is a polyketone tire cord which exhibits excellent elongation and strength and is produced by using a polyketone copolymer made of both carbon monoxide and at least one type of olefin-based unsaturated hydrocarbon. Also provided is a production method thereof.

Description

[0001] The present invention relates to a polyketone tire cord,

The present invention relates to a polyketone tire cord, and more particularly, to a polyketone composition having improved strength of a tire when exposed at a high temperature.

Conventional radial tires consist of a polyethylene terephthalate or a carcass ply reinforced with a fiber cord such as rayon or the like, and a belt structure reinforced with a steel cord.

In the first pneumatic tires, canvas paper made of cotton was used as carcass material, and fiber cords such as rayon, nylon, and polyethylene terephthalate were used as carcass ply materials according to the development of man-made fibers. Recently, Code and so on.

In general, polyethylene terephthalate is widely used as an air inlet radial tire, more specifically, as a carcass ply material of an air inlet radial tire having a flatness ratio of 0.65 to 0.82. In addition, a flat ratio is low, more specifically, Rayon is used as a carcass ply reinforcement of high-speed air inlet radial tires. Although some of the polyethylene terephthalate is used for radial tires having a high flatness and low flatness ratio, the toughness is superior to that of rayon, but its adhesion to rubber is low, and its high temperature properties and shape stability are insufficient.

In order to overcome these problems, aramid fibers having higher physical properties and morphological stability than polyethylene terephthalate have been recently used. However, they have a strong strength as compared with rayon, but their adhesion to rubber is low.

In the case of general rayon, the adhesive strength to rubber is superior to that of polyester fiber, but in terms of physical properties, there is a disadvantage that the strength is low and therefore the tire cord is not suitable as well as the tire weight is increased when applied to the tire.

Due to the above-described problems, conventional tires using rayon as carcass have been limited in their use despite their excellent shape stability and high temperature properties.

Korean Patent No. 10-1205940 Korean Patent No. 10-0607086

In order to solve the above problems, it is an object of the present invention to provide a polyketone tire cord having excellent strength, which is produced by using a polyketone copolymer composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, and a process for producing the same do.

The present invention relates to a composition comprising a copolymer comprising at least 90% by weight of a copolymer of carbon monoxide and one or more olefins and having a molecular weight distribution of 1.5 to 3.5, an intrinsic viscosity of 5 to 7 dl / g, an initial modulus value of 100 g / , Elongation at 6.0 g / d of 3.0 to 4.0, and elongation of at least 0.5% at 11.0 g / d or more.

Further, the present invention provides a polyketone tire cord characterized in that the strength of the polyketone tire cord is 11 g / d or more.

In addition, the present invention provides a tire comprising the polyketone tire cord, wherein the polyketone tire cord is contained in a carcass ply or a cap ply.

In addition, the present invention relates to a method for producing a polyurethane foam, which comprises treating an undrawn product made of a polyketone copolymer with a heat stabilizer, drying the product in a hot roll type, further treating the heat- The present invention also provides a method for producing the polyketone tire cord manufactured by spinning a drawn yarn.

More specifically, the present invention provides a method for producing a polyketone tire cord characterized in that it is stretched 1.1 to 2.0 times in the washing step in the production of the polyketone undrawn yarn.

The present invention is to prepare a polyketone solution from carbon monoxide, an ethylene and a propylene copolymer, and to provide a polyketone fiber having excellent strength from the polyketone solution. The polyketone tire cord produced according to the present invention is suitable for use as a bar tire having excellent strength and elongation.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view schematically showing the role of a heat-resistant stabilizer according to the prior art. FIG.
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.
6 is a schematic view schematically showing the structure of a tire for a passenger car manufactured using a polyketone dip cord according to the present invention.
7 is a force-strain curve of the present invention and a conventional hot-air drying type dip cord.

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.

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 compounds include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, 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 preferable in the present invention, is p-toluenesulfonic acid, which has high catalytic activity when used with a mixed solvent of acetic acid and water as a liquid medium, It becomes possible to produce a polyketone having a high intrinsic viscosity suitable for the polyolefin.

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, tricyclo undecene, 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 tire cord, and 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, 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 most preferred polyketone has a molecular weight distribution of 1.5 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.

The polyketone tire cord made of the polyketone preferably has a tensile strength lowering rate of 20% or less after being treated at 150 ° C for 30 minutes in order to test a high temperature occurring during traveling, 20 g / d is preferable. Particularly, the polyketone tire cord of the present invention has a strength of 11 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 the water bath is maintained at about 0 to 80 ° C to prevent the deterioration of the physical properties due to the formation of pores in the fiber structure due to the 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 apparatus. In this case, the drying temperature and the drying method have a great influence on the post-processing and physical properties of the filament.

Then, the filament passing through the drying device is finally wound in the winder through the 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, particularly a hot-roll drying method, and performing a stretching process in the course of washing the fibers in the range of 1.1 to 2.0 times, preferably 1.2 to 1.6 times, more preferably 1.4 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.

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 wt%. If the concentration of the metal salt is less than 30% by weight, the solubility is lowered. If the concentration of the metal salt is more than 80% by weight, the cost for concentration is increased, 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. An orifice having a diameter of 100 to 500 mu m and a length of 100 to 1500 mu m, wherein the ratio of the diameter to the length (L / D) is 1 to 3 to 8 times, The spinning stock solution is extruded and spun through a spinning nozzle containing a plurality of orifices having an interval of 1.0 to 5.0 mm to allow the fiber spinning solution to pass through the air layer to reach the coagulation bath and solidify to obtain a multifilament.

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, If the diameter of the nozzle orifice is less than 100 탆, a large number of yarn breaks occur at the time of spinning, which adversely affects radioactivity. If the diameter exceeds 500 탆, the coagulation speed of the solution in the spinning coagulation bath is slow, And water washing becomes difficult.

The number of orifices is set to 100 to 2,200, more preferably 300 to 1,400, in consideration of the orifice interval for uniform cooling of the solution, taking into account the fact that it is for industrial use, particularly for tire cords.

If the number of orifices is less than 100, the fineness of each filament becomes thick and the solvent can not sufficiently escape within a short time, so that the coagulation and flushing can not be completely performed. If the number of orifices is more than 2,200, adjacent filaments are likely to be formed in close contact with each other in the air layer section, and the stability of each filament after spinning is deteriorated, resulting in deterioration of physical properties. In addition, .

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 multifilament produced by the method according to the present invention is a polyketone multifilament with a total denier range of 500 to 3,500 and a breaking load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2,200 individual filaments with a fineness of 0.5 to 8.0 denier.

The fiber density of the monofilament is 1.295 to 1.310 g / cm < 3 > by the hot-rolling method of the present invention and the step of adding the heat-resistant stabilizer, and the structure thereof is as shown in Fig. As a result, the initial modulus value of the polyketone monofilament prepared by the above process is 200 g / d or more, elongation at 2.5 g / d at 2.5 g / d and elongation at least 0.5% at 19.0 g / d or more.

In the present invention, the wound cord is twisted by a twisting machine to produce a cord, and the cord is dipped into a dipping solution to provide a tire cord and a tire.

The polyketone multifilament produced by the above method is obtained by twisting two wound yarns with a direct twisted yarn in which the twisted yarn and the twin yarn are simultaneously wound to produce a raw cord for a tire cord, '. The raw cord is manufactured by applying a ply twist to a polyketone yarn for a tire cord and then applying and twisting the cable twist. Generally, the upper and lower bristles are subjected to the same softening or different softening depending on necessity.

An important result of the present invention is that the physical properties such as the strength of the cord, the tensile strength and the fatigue resistance of the cord are changed according to the degree of twisting (number of years) given to the polyketone multifilament. Generally, when the twist is high, the strength decreases, and the midline and the twist tend to increase. My fatigue shows a tendency to improve with increasing kinks. The softening point of the polyketone tire cords manufactured according to the present invention was 200/200 TPM to 500/500 TPM at the same time, and the upper and lower edges were given the same numerical values, indicating that the tire cords produced were rotated or twisted So that it is easy to maintain a straight line image, thereby maximizing the manifestation of physical properties. In this case, when the stress is less than 200/200 TPM, the loss of the cord is decreased and the fatigue is liable to be lowered. If the stress is more than 500/500 TPM, the tensile strength is large.

The produced 'Raw Cord' is woven using a weaving machine, and the resultant fabric is dipped in the dipping solution and then cured to form a tire cord with a resin layer on the 'Raw Cord' surface 'Dip Cord' is manufactured.

The dipping process of the present invention will be described in more detail. Dipping is accomplished by impregnating the surface of the fiber with a resin layer called RFL (Resorcinol-Formaline-Latex) . In the case of using PET fiber, since the reactor on the surface of the PET fiber is smaller than that of the rayon fiber or the nylon fiber, the surface of the PET is first activated before the bonding treatment is performed (2 bath dipping). The polyketone multifilament according to the present invention uses a 1-bath dipping. Dip bathing uses a known dip bath for tire cords.

The dip cord manufactured according to the method described above can be advantageously used as a tire cord for a passenger car having a total denier of 1000 to 6000 dia. And a cutting load in the range of 14.0 to 35.0 kg.

Further, the polyketone dip cord manufactured according to the present invention is used as a material for a carcass ply or a cap ply of air inlet radial tires.

Specifically, a code as shown in Fig. 6 is produced. More specifically, the carcass cord 13 using the polyketone dip cord manufactured according to the present invention has a total denier of 2,000 to 8,000. The carcass ply 12 includes at least one layer of carcass ply reinforcing tire cord 13. It is preferable that the dipped cord reinforcing density of the carcass ply is 15 35 EPI. If the reinforcing density is less than 15 EPI, the mechanical properties of the carcass ply drop sharply. If the reinforcing density exceeds 35 EPI, it is disadvantageous in terms of economy.

The carcass ply 12 having radially outer flyturn-up 14 preferably comprises a carcass cord of one layer and two layers. The reinforcing carcass cord 13 is oriented at an angle of 85 to 90 degrees with respect to the circumferential intermediate surface of the tire 11. [ In the particular embodiment shown, the reinforcing carcass cords 13 are arranged at 90 [deg.] With respect to the circumferential intermediate plane. In the case of the fly turn-up 14, it is preferable to have a height of about 40 to 80% with respect to the maximum cross-sectional height of the tire. If the fly turn-up is less than 40%, the stiffening effect of the tire side wall is too low. If the fly side turn-up is less than 40%, the tire side wall stiffness is too high.

The bead regions 15 of the tire 11 each have an annular bead core 16 that is non-stretchable. The bead core is preferably made of a single or single filament wire wound continuously. In a preferred embodiment, a high strength steel wire having a diameter of 0.95 mm to 1.00 mm forms a 4x4 structure, and it is also possible to form a 4x5 structure.

In a particular embodiment of the present invention, the bead region also has a bead filler 17, which, in the case of the bead filler, needs to have a hardness above a certain level, preferably a Shore A hardness of 40 or higher.

In the present invention, the crown portion is reinforced by the belt 18 and the cap ply 19 structure. The belt structure 18 includes two cut belt ply 20 and the cord 21 of the belt ply is oriented at an angle of about 20 degrees with respect to the circumferential center plane of the tire. The cord 21 of the belt ply is disposed opposite to the direction of the cord 22 of the other belt ply, in the direction opposite the circumferential center plane. However, the belt 18 may comprise any number of plys, and may preferably be arranged in a range of 16 to 24 degrees.

The belt 18 serves to provide lateral stiffness to minimize the rise of the tread 23 from the road surface during operation of the tire 11. [ The cords 21 and 22 of the belt 18 are made of steel cords and have a 2 + 2 structure, but may be of any structure.

The cap ply 21 and the edge ply 24 are reinforced on the upper portion of the belt 18 so that the cap ply cords 25 in the cap ply 19 are reinforced in parallel with the circumferential direction of the tire, The cap fly cords 25 having a function of suppressing the size change in the circumferential direction and having a large heat shrinking stress at a high temperature are used. One cap ply 19 and one ply edge ply 21 may be used, but preferably cap ply of one or two layers and edge ply of one or two layers are also reinforced. The cap fly cord may use a polyketone dip cord manufactured according to the method of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art

Example 1

A polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 / g was injected into an extruder maintained at 35 DEG C at an injection temperature of 25 DEG C with a gear pump at a rate of 13500 g / The extruder was injected at a rate of 1100 g / hour by means of a screw feeder. The residence time in the swelling zone of the extruder was set to 0.8 minutes and the temperature was raised to 30 to 40 ° C. to sufficiently dissolve the polyketone powder in the metal salt solution. Polyketone fibers were prepared by dry-wet spinning by maintaining the block temperature at 50-60 < 0 > C and operating the screw at 200 rpm.

At this time, a circular nozzle having an odd number of nozzles of 500 and a diameter of 0.2 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 7.5% by weight, and it was in a homogeneous state in which the undissolved polyketone particles were not contained.

The fiber thus obtained was subjected to a drawing at 1.4 times in the washing process. Before drying, the heat-resistant stabilizer was dip-dipped in a 0.1% solution of Adeka's AO80 and methanol as a phenolic heat stabilizer in a mixed solution of Adeka at a total draw ratio of 16.4 The fibers were subjected to 1 to 7 times of stretching and 2.5 to 2.5 times of stretching, and the 2-stage stretching comprised 1.5, 1.35 and 1.2 times of 3-step stretching, and the respective steps were 240, 255, 265 and 268 Lt; 0 > C. The produced multifilament was twisted in three strands to produce a polyketone tire cord.

Table 2 shows the tire cord after the above process.

Example 2

The same as Example 1 except that the temperature of each step of the two stages in the hot-roll drying was adjusted to 240, 250, 260 and 268 캜.

Example 3

The same procedure as in Example 1 was carried out except that the temperature of each step of the two stages was adjusted to 240, 255, 265 and 272 캜 in the hot-roll drying.

Example 4

A polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 5.7 g was injected into an extruder maintained at 35 DEG C at an injection temperature of 25 DEG C at a feeding rate of 13500 g / The extruder was injected at a rate of 1100 g / hour by means of a screw feeder. The residence time in the swelling zone of the extruder was set to 0.8 minutes and the temperature was raised to 30 to 40 ° C. to sufficiently dissolve the polyketone powder in the metal salt solution. Polyketone fibers were prepared by dry-wet spinning by maintaining the block temperature at 50-60 < 0 > C and operating the screw at 200 rpm.

The obtained fibers were subjected to a drawing at 1.4 times in a washing process, and a heat stabilizer was dipped in a 0.1% solution of Adeka's AO80 and methanol as a phenolic heat stabilizer before drying, followed by hot roll drying and heating chamber method Total stretching magnification: 16.4 times, fibers were stretched from one stage to seven times, and the second stage was stretched to 2.5 times. The second stage includes 3 step stretching of 1.5, 1.35, and 1.2 times, 255, 265 and 268 < 0 > C. The produced multifilament was twisted in three strands to produce a polyketone tire cord.

Table 2 shows the tire cord after the above process.

Example 5

The same as Example 4 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 / g.

Example 6

And the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 / g.

Example 7

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 35 캜 at an injection temperature of 25 with a gear pump at a rate of 13,500 g / hr. The polyketone powder having a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 / The extruder was injected at 1100 g / hour into the extruder, and the residence time in the extruder swollen zone was set to 0.8 minutes and the temperature was raised to 30 to 40 DEG C to sufficiently dissolve the polyketone powder in the metal salt solution. Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 50-60 < 0 > C and operating the screw at 200 rpm.

Table 2 shows the tire cord after the above process.

Example 8

The same as Example 7 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 9

And the molecular weight distribution of the polyketone polymer was adjusted to 3.5.

Example 10

The procedure of Example 1 was repeated except that a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer was subjected to 1 dip before drying.

Example 11

Example 1 was the same as Example 1 except that a 0.1% solution of AO80 and methanol of Adeka Co. as a phenolic heat stabilizer was subjected to two dipping before drying and before drawing.

Comparative Examples 1 to 3

The fiber was produced in the same manner as in Example 1 except that the hot-roll drying method was used instead of the hot-roll drying method.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Hot air dryer temperature (캜) 220 260 300 Intrinsic Viscosity of Polyketone (IV) 6.0 6.0 6.0 Molecular weight distribution of polyketone (MWD) 3.3 3.3 3.3

Property measurement

(1) intrinsic viscosity

0.1 g of the sample was dissolved in a reagent (90 ° C) mixed with phenol and 1,1,2,2-tetrachloroethanol 6: 4 (weight ratio) for 90 minutes, transferred to a Ubbelohde viscometer, For 10 minutes, and use a viscometer and an aspirator to determine the number of drops of the solution. The number of drops of solvent The RV value and the IV value were calculated by the following equation obtained by the same method as described above

R.V. = Sample falling water / solvent falling water water

I.V. = 1/4 x [(R.V.- 1) / C] + 3/4 x (In R.V./C)

In the above equation, C represents the concentration (g / 100 ml) of the sample in the solution.

(2) Molecular weight distribution

A polyketone was dissolved in a hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate so as to have a polyketone concentration of 0.01% by weight and measured under the following conditions.

Device: SHIMADZU LC-10Advp

Column: Use the following columns in the order of (a), (b) and (c).

(A): Shodex GPCHFIP-G

(B): Shodex HFIP-606M

(C): Shodex HFIP-606M

Column temperature: 40 ° C

Mobile phase: hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate

Flow rate: 0.5 ml / min

Detector: differential refractometer

Injection volume: 30 μl

As a standard sample, polymethyl methacrylate (PMMA) having a monodispersed molecular weight distribution was used (concentration: 0.01% by weight), and the weight of the polyketone in terms of PMMA measured from the calibration curve of PMMA obtained under the same conditions as the above- The average molecular weight (Mw) and the number average molecular weight (Mn) were determined, and Mw / Mn was determined as a molecular weight distribution.

(3) Method of measuring modulus and strength of tire dip cord

The prepared tire dipped cords were left in a standard temperature condition, that is, in a constant temperature and humidity room at 25 ° C and a relative humidity of 65% for 24 hours, and then the samples were measured by a tensile tester using the ASTM 2256 method. The physical properties of the dipped cords were measured with the average values of the remaining eight, excluding the maximum value and the minimum value, respectively, out of the ten values measured from ten dipped cords. The initial modulus represents the slope of the graph before the yield point.

(4) Workability

Observe for 24 hours at one position to determine the number of thread trimming occur on the roller.

Tire dip code A kite Strength (g / d) Shinto (%) Initial modulus (g / d) 6.0g / d Elongation at stress (%) 11.0 g / d ~ Elongation (%) when stressed to cut Workability
(Number / day positon) Example 1 12.55 6.9 110 3.3 1.2 1.2 Example 2 13.00 6.5 130 3.0 1.0 0.5 Example 3 12.85 6.7 125 2.1 1.1 1.3 Example 4 12.45 7.1 104 3.2 0.9 0.9 Example 5 12.90 6.7 108 2.1 1.1 0.5 Example 6 12.55 6.9 110 3.3 1.2 0.7 Example 7 12.55 6.9 110 3.3 1.2 1.1 Example 8 13.00 6.5 130 3.0 1.0 0.8 Example 9 12.85 6.7 125 2.1 1.1 0.6 Example 10 12.55 6.9 110 3.3 1.2 1.2 Example 11 13.00 6.5 130 3.0 1.0 0.7 Comparative Example 1 9.74 5.3 95 3.8 0 3 Comparative Example 2 10.20 5.1 100 3.7 0 4 Comparative Example 3 10.01 5.0 98 3.9 0 5

As shown in Table 2, the dip cord manufactured according to the embodiment of the present invention is excellent in elongation and strength and is suitable for use as a tire dipped cord using the dip cord.

Claims

Carbon monoxide and one or more olefins, having a molecular weight distribution of 1.5 to 3.5, an intrinsic viscosity of 5 to 7 dl / g, an initial modulus value of 100 g / d or more, A polyketone tire cord elongation at 6.0 g / d of 3.0 to 4.0% and at least 11.0 g / d of at least 0.5%.

The method according to claim 1,
Wherein the strength of the polyketone tire cord is 11 g / d or more.

A tire comprising the polyketone tire cord according to any one of claims 1 to 2.

The method of claim 3,
Characterized in that the polyketone tire cord is contained in a carcass ply or a cap ply.

A non-drawn filament made of a polyketone copolymer is treated with a heat-resistant stabilizer and then dried in a hot-roll type. The unstretched filament is further treated with a heat-resistant stabilizer and then stretched to produce a drawn filament. The method of producing the polyketone tire cord according to the above 1, which is manufactured.

6. The method of claim 5,
Wherein the polyketone is stretched to 1.1 to 2.0 times in the washing step in the production of the polyketone undrawn yarn.