KR20160139396A - Polyketone spunbond non-woven including polyketone fiber method for manufacturing the same - Google Patents

Abstract

The present invention relates to a spun-bonded non-woven fabric made of polyketone fibers, and to a production method thereof. More specifically, the present invention relates to a spun-bonded non-woven fabric which exhibits outstanding tensile strength since the spun-bonded non-woven fabric is made of polyketone fibers, and to a production method thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spunbonded nonwoven fabric made of polyketone fibers and a method of producing the same.

The present invention relates to a spunbonded nonwoven fabric made of polyketone fibers and a method for producing the spunbonded nonwoven fabric. More particularly, the present invention relates to a spunbonded nonwoven fabric made of polyketone fibers and having excellent tear strength, and a method for producing the same.

Spunbonded nonwoven fabrics made of polyester resin are widely used because of their various uses. Such spunbonded nonwoven fabrics are used for building materials, filtration devices, furniture and wickets because of their excellent strength and penetration characteristics, and recently they are also used particularly as agricultural vinyl houses.

Spunbond nonwoven fabrics are used for disposable medical gowns and gloves because they can prevent the invasion of bacteria such as bacteria and prevent them from being contaminated. The spunbonded nonwoven fabric of this kind may be produced by a method such as meltblown, or a general spunbond nonwoven fabric may be used for the inside, and a web having excellent tactile feeling may be used for the outer cover by a meltblown method. Such spunbond nonwoven fabrics are described in U.S. Patent 4,041,203 and U.S. Patent 4,863,785. In recent years, the use of spunbonded nonwoven fabrics for agricultural use has been increasing steadily as the use of vinyl houses has exploded. The spunbonded nonwoven fabric is excellent in thermal insulation because of its large internal space in the structure, and its production method is simple, so it is easy to mass-produce small kinds of spunbond nonwoven fabric.

However, when a spunbonded nonwoven fabric made of a polyester resin is used as an agricultural vinyl house, the polymer chains are cut off by ultraviolet rays, resulting in deterioration of mechanical properties or destruction of the structure of dyes and pigments existing as polymer chains, resulting in discoloration or discoloration There is a problem.

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. Further, after the polymerization, complicated Pd extraction treatment is required, and industrially can not be employed from the viewpoints of productivity and cost. International publication WO 00/09611 discloses polyketones having a Pd content of 5 ppm. However, since the polyketone is obtained by removing Pd in the polymer after polymerization 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 aims to provide a spunbonded nonwoven fabric having excellent tear strength by producing a spunbonded nonwoven fabric using polyketone fibers and a method for producing the same.

In order to attain the above object, the present invention provides a poly (ethylene oxide) copolymer comprising repeating units represented by the following general formulas (1) and (2) and having y / x of 0.01 to 0.5 and an intrinsic viscosity of 1 to 3 dl / A spunbonded nonwoven fabric characterized by comprising a polyketone fiber including a ketone polymer.

- [- 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)

At this time, it is more preferable that the polyketone copolymer has a molecular weight distribution of 1.5 to 4.0.

The spunbonded nonwoven fabric has a strength of 15 g / d or more and a tear strength of 10 kg or more.

The present invention also relates to a process for producing a filament, comprising the steps of spinning and drawing a polyketone in a spinneret, respectively, to produce a filament; Opening the filament and laminating it in the form of a web; And thermally adhering the filaments of the laminated web to fix the web to produce a spunbonded nonwoven fabric.

Here, the polyketone has an intrinsic viscosity of 1.0 to 3.0 dl / g.

The present invention can provide a spunbonded nonwoven fabric having excellent tear strength by producing a spunbonded nonwoven fabric 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 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.

In particular, the anion (c) of the acid having a pKa of 4 or less, which is preferred in the present invention, is p-toluenesulfonic acid, which, when used in combination with a mixed solvent of acetic acid and water as a liquid medium, 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. As the molar ratio of propylene becomes larger, it is unsuitable as a nonwoven fabric, and the molar ratio of ethylene to propylene is preferably 100: 0 to 70:10.

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 device is preferably 1.0 dl / g to 2.0 dl / g. At this time, when the intrinsic viscosity of the polyketone polymer is less than 1.0, the mechanical strength is lowered during production into fibers, and when the polyketone polymer is more than 3.0, the workability is lowered.

The polyketone spunbonded nonwoven fabric made of polyketone has a strength of 15 g / d or more and a tear strength of 10 kg or more.

A method for producing the polyketone spunbonded nonwoven fabric of the present invention will be described.

A method for producing a polyketone spunbonded nonwoven fabric according to the present invention comprises the steps of spinning and drawing a polyketone in a spinneret to produce filaments; Opening the filament and laminating it in the form of a web; And fixing the web by thermally adhering the filaments of the laminated web to produce a spunbonded nonwoven fabric.

At this time, the heat bonding is preferably performed for 3 to 9 seconds using a hot air drier, but 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. The content of the palladium catalyst in the multifilament prepared in Examples and Comparative Examples was measured by high frequency plasma emission spectrochemical analysis.

Example 1

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 80 ° C and the second stage at 84 ° C are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0.

The polyketone terpolymer prepared above was dissolved and spun in a conventional spunbond manufacturing apparatus. Thereafter, the spun filaments were integrated on a moving net conveyor, and then subjected to heat-bonding treatment using a calender roll, followed by hot-air treatment using a hot air blower, and wound around a winding machine to produce a spunbonded nonwoven fabric.

Example 2

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 占 폚 and 84 占 폚 are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.6 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0.

The polyketone terpolymer prepared above was dissolved and spun in a conventional spunbond manufacturing apparatus. Thereafter, the spun filaments were integrated on a moving net conveyor, and then subjected to heat-bonding treatment using a calender roll, followed by hot-air treatment using a hot air blower, and wound around a winding machine to produce a spunbonded nonwoven fabric.

Example 3

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 9 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 74 deg. C and the second stage at 84 deg. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 2.0 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0.

The polyketone terpolymer prepared above was dissolved and spun in a conventional spunbond manufacturing apparatus. Thereafter, the spun filaments were integrated on a moving net conveyor, and then subjected to heat-bonding treatment using a calender roll, followed by hot-air treatment using a hot air blower, and wound around a winding machine to produce a spunbonded nonwoven fabric.

Comparative Example  One

A polyester chip having an intrinsic viscosity of 0.655 was melted and spun in a conventional spunbond manufacturing apparatus. Thereafter, the spun filaments were integrated on a moving net conveyor, and then subjected to heat-bonding treatment using a calender roll, followed by hot-air treatment using a hot air blower, and wound around a winding machine to produce a spunbonded nonwoven fabric.

Experimental Example 1

The properties of the nonwoven fabric prepared in each of 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) 12.0 11.2 11.0 7.7 Shinto (%) 5.6 5.8 6.0 51 Tear strength (kg) MD 11 10 11 9 CD 10 10 11 8

As can be seen from the above Table 1, the spunbonded nonwoven fabric prepared in Examples 1 to 3 exhibited excellent improvement in strength and elongation as compared with Comparative Example 1, and tear strength was also improved.

Claims (6)

A spunbonded nonwoven fabric comprising a polyketone fiber comprising a repeating unit represented by the following general formulas (1) and (2) and comprising a polyketone polymer having y / x of 0.01 to 0.5.
- [- 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 copolymer has a molecular weight distribution of 1.5 to 4.0. The method according to claim 1,
The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is a bis (bis (2-methoxyphenyl) -1,3-dioxane-5,5- Wherein the spunbonded nonwoven fabric is a spunbonded nonwoven fabric. The method according to claim 1,
Wherein the spunbonded nonwoven fabric has a tear strength of 10 kg or more. Preparing filaments by spinning and stretching the polyketone respectively in a spinneret;
Opening the filament and laminating it in the form of a web; And
And thermally adhering the filaments of the laminated web to fix the web, thereby producing a spunbonded nonwoven fabric. 6. The method of claim 5,
Wherein the polyketone has an intrinsic viscosity of 1.0 to 3.0 dl / g.

Images