KR101684892B1 - Polyketone resin blend for ATM gear - Google Patents

Abstract

The present invention relates to a polyketone resin composition for ATM gears containing 0.1 to 15 parts by weight of a layered clay filler based on 100 parts by weight of a polyketone resin, and is excellent in retention of physical properties and abrasion resistance.

Description

Technical Field [0001] The present invention relates to a polyketone resin blend for ATM gear,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone resin composition for use in parts such as helical gears of automatic teller machine (ATM), and more particularly, to a polyketone resin composition for use in parts such as a blend of a linear alternating polyketone and a mineral filler composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon The present invention relates to a polyketone resin composition for an ATM gear.

Generally, polyoxymethylene (hereinafter referred to as "POM") has a high mechanical strength and is very advantageous in rigidity, creep resistance, chemical resistance, chemical resistance, and sliding properties. Due to the advantages described above, it is widely regarded as a representative engineering plastic in automobile parts, electrical and electronic equipment parts, and industrial fields.

Particularly, the abrasion resistance is very excellent and it is often applied to applications such as spur gears, helical gears, and worm gears. POM itself satisfies some degree of mechanical properties and abrasion resistance. However, there is a problem that this part of the gear is damaged when driven under high load, and when it is applied to a rotating part, the crystallization degree is higher than that of other engineering plastics and the shrinkage ratio is large It may cause noise due to the problem of dimensions. Accordingly, it has become necessary to improve rigidity, abrasion resistance, and shrinkage characteristics.

Conventionally, various lubricants have been studied for the purpose of improving wear resistance of the POM resin. In particular, many studies have been conducted to improve the abrasion resistance at high load by incorporating a lubricant. For example, in Japanese Patent Publication No. 67-21786, a method of adding petroleum-based lubricating oil or synthetic lubricating oil to ultra high molecular weight polyethylene was introduced,

In the publication No. 72-41092, a composition in which an ester-based lubricating oil is added to a polycarbonate resin was introduced. However, in this case, there is a problem that stiffness is remarkably deteriorated and can not be used for applications requiring rigidity, and the added lubricant has a problem of being exposed on the surface of the product.

Further, Japanese Patent Publication No. 73-37572 discloses a composition in which an unsaturated higher fatty acid, a salt of an unsaturated higher fatty acid, an ester, an amide, a chloride or a metal soap is additionally added. This composition, too, I can not solve it.

Korean Patent Publication No. 1991-0010024 discloses a composition in which potassium titanate and a lubricant are added. In this case, sufficient rigidity can be obtained, but it is necessary to improve the characteristics of abrasion resistance and shrinkage anisotropy.

Another technology, Patent No. 10-0855130, discloses a composition comprising (a) 100 parts by weight of a polyoxymethylene resin, (b) 0.1 to 30 parts by weight of a layered clay filler, (c) 0.1 to 10 parts by weight of silicone oil, and (d) Or 0.01 to 5 parts by weight of neoalkoxysilicate as a polyoxymethylene resin composition, which can be used as a helical gear or the like. With the above-described structure, it is possible to manufacture a gear having a high flexural modulus, a constant mold shrinkage rate, excellent shrinkage anisotropy, rigidity, and low noise.

However, even if the above-mentioned polyoxymethylene resin is used, it is a reality that the abrasion resistance can not be improved. Therefore, fundamental problems related to the durability of ATM are not solved, and troubles such as occurrence of frequent faults due to long-term use, additional costs due to the replacement of parts due to long-term use, and generation of complaints from customers are constant.

Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

In order to solve the above problems, it is an object of the present invention to provide a polyketone resin composition for an ATM gear comprising a polyketone copolymer and a clay filler.

In order to achieve the above technical object, a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) is produced by injection molding a polyketone copolymer having y / x of 0.03 to 0.3 Wherein the polyketone resin composition contains 0.1 to 15 parts by weight of a silicone resin per 100 parts by weight of the polyketone resin.

- (CH2CH2-CO) x- (1)

- (CH2CH (CH3) -CO) y- (2)

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

The polyketone resin composition for ATM gear of the present invention is superior in durability, especially abrasion resistance, compared with gears made of conventional polyoxymethylene (POM) resin composition, resulting in frequent failures due to long-term use and additional costs due to parts replacement And the like can be solved.

Hereinafter, the present invention will be described in detail.

The present invention relates to a polyketone resin composition for ATM gears, which comprises 0.1 to 15 parts by weight of a layered clay filler based on 100 parts by weight of a polyketone resin.

1. Polyketone polymer composition

The polyketone polymer of the present invention is a linear alternating structure and substantially contains carbon monoxide per one molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. Ethylenically unsaturated hydrocarbons can also be selected from the group consisting of ethene and alpha-olefins such as propene, 1-butene, iso-butene, 1- hexene, 1- octene, , Or an aryl aliphatic group containing an aryl substituent on another aliphatic molecule, particularly containing an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons in ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene. The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene or a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

Preferred polymeric rings of the polyketone polymers in the present invention can be represented by the following formula (1).

[Chemical Formula 1]

- [CO- (-CH2-CH2-)] x- [CO- (G)] y-

In the above formula (1), G is an ethylenically unsaturated hydrocarbon, particularly an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and y / x is preferably 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

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

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

In addition, the melting point of the polymer can be controlled by controlling the ratio of ethylene to propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, the melting point is about 220 ° C, while the melting point is adjusted to 235 ° C when the molar ratio is adjusted to 47.3: 2.7: 50.

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 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability is deteriorated.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is 2.5 or more, the moldability is poor. 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.

 A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. In the presence of a catalyst composition suitably produced from an anion of a non-hydrohalogenic acid having a pKa of less than 6 or preferably less than pKa < 2 > and a bidentate ligand of phosphorus (measured in water at 18 DEG C), carbon monoxide and a hydrocarbon monomer Is contacted under polymerization conditions to prepare a polyketone polymer.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. The carbon monoxide and the hydrocarbon monomer are brought into contact under polymerization conditions in the presence of a catalyst composition suitably produced from a palladium compound, an anion of a hydrohalogenic acid having a pKa of 6 or less, preferably less than pKa 2, and a bidentate two-coordinate ligand, to produce a polyketone polymer.

As the production method of the polyketone resin, liquid phase polymerization in which carbon monoxide and olefin are carried out in an alcohol solvent through a catalyst composition composed of a palladium compound, an acid having 6 or less of PKa, and a ligand compound of phosphorus can be employed. The polymerization temperature is preferably from 50 to 100 ° C. and the reaction pressure is from 40 to 60 bar. The polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

This is preferred as palladium acetate and a palladium compound in the amount of 10 ^-3 to ^10-2 1mole preferred. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid is used and its amount is preferably 6 to 20 equivalents based on palladium. Also, 1,3-bis [di (2-methoxyphenylphosphino)] propane is preferably used as the left-handed compound of phosphorus, and the amount to be used is preferably 1 to 1.2 equivalents based on palladium.

Hereinafter, the polymerization process of the polyketone resin will be described in detail.

The repeating unit derived from carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, especially repeating units derived from carbon monoxide, and ethylenically unsaturated compounds and repeating units derived from propylenically unsaturated compounds are substantially Are excellent in mechanical properties and thermal properties, excellent in processability, high in abrasion resistance, chemical resistance and gas barrier property, and are useful materials for various applications. It is considered that the high molecular weight product of the copolymerized polyketone having three or more members is more useful as an engineering plastic material having higher workability and thermal properties and having excellent economy. Particularly, it has high abrasion resistance and can be used in light gasoline tanks because of high gas barrier properties such as parts of gears of automobiles, high chemical resistance, and lining materials of chemical transport pipes. In the case of using an ultrahigh molecular weight polyketone having an intrinsic viscosity of 2 or more as the fiber, it is possible to conduct stretching at a high magnification and to have a high strength and a high modulus of elasticity oriented in the stretching direction as belts, reinforcements of rubber hoses, tire cords, And is suitable for use in building materials and industrial materials.

The production method of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15 elements, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

The catalyst used in the polyketone polymerization of the present invention is characterized by being composed of (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15 elements.

(a) Examples of Group 9, Group 10 or Group 11 transition metal compounds include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include cobalt acetate, cobalt Acetyl acetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, ruthenium trifluoromethanesulfonate. Nickel, or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate, complexes of copper or silver, carbonates, phosphates, carbamates and sulfonates. Specific examples thereof include copper acetate, And copper acetate, copper acetylacetate, acetic acid silver, trifluoroacetic acid silver, silver acetylacetate, trifluoromethanesulfonic acid and the like.

Among them, (a) the ninth, tenth, or eleventh group transition metal compound preferable from the viewpoint of yield and molecular weight of the polyketone is a palladium compound, and palladium acetate is more preferable.

(b) an example of a ligand having an atom of Group 15 is bis (bis (2-methoxyphenyl) -1,3-dioxane-5,5- Phosphin), 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-biphenyl- (Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3- Bis (di (2-methoxyphenyl) phosphino] propane, 1,3-bis [di Bis (diphenylphosphino) benzene, 1, 2-bis (diphenylphosphino) cyclohexane, bis (di (2-methoxy- Bis [[di (2-methoxy-phenyl) methyl] benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, Phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3 And phosphorus ligands such as bis [di (2-methoxyphenyl) phosphino] propane and 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane.

 Among them, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of the yield of polyketone are ((2,2-dimethyl- Bis (di (2-methoxyphenyl) phosphino] propane, 1 (3-dioxane-5,5-diyl) bis (2-methoxyphenyl) phosphino] methyl] benzene in view of the molecular weight of the polyketone, and 2-hydroxy [ (2,2-dimethyl-1, 3-bis [di (2-methoxyphenyl) phosphino] propane in view of safety without requiring an organic solvent, Di (2-methoxy-4-sulfonic acid sodium-phenyl) -bis (bis (methylene) (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] methyl] benzene, and most preferably (( (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).

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. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per 1 mol of the transition metal compound (a).

Further, the addition of benzophenone in the polymerization of the polyketone is another characteristic. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It is not preferable because it tends to decrease

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

 The ternary copolymerization of carbon monoxide, the ethylenically unsaturated compound and propene is carried out in the presence of an organometallic complex catalyst comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) and group 15 element , Wherein the catalyst is produced by contacting the two components. Any method may be employed as the method of contacting. That is, the solution may be prepared as a solution in which two components are premixed in a suitable solvent, or the two components may be supplied separately to the polymerization system and contacted in the polymerization system.

 As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

A linear alternating polyketone is formed by the polymerization method as described above.

2. Silicone resin

In the present composition, the silicone resin is characterized by containing 0.1 to 15 parts by weight of a silicone resin per 100 parts by weight of the polyketone resin. When the content of the silicone resin is less than 0.1, wear resistance is not sufficient when used as a gear, and when the content exceeds 15, mechanical properties inherent to polyketone are deteriorated.

The silicone resin used in the present invention is in the form of a powder and preferably has a diameter of 1 to 2 占 퐉. When the silicone resin is out of the range, blending with a polyketone is not smooth.

3. Manufacturing Method

Hereinafter, a method for manufacturing an ATM gear using the polyketone resin composition as described above will be described.

A method of manufacturing an ATM gear using the polyketone resin composition of the present invention comprises: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing acetic acid and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And mixing and extruding the polyketone resin with a mineral filler.

As the palladium compound constituting the catalyst composition, palladium acetate can be used, and the amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole.

As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.

As the 2-position ligand compound constituting the catalyst composition, bis (2, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) bis (bis (2-methoxyphenyl) ), 1,3-bis [diphenylphosphino] propane (such as 1,3-bis [di (2-methoxyphenylphosphino)] propane and 1,3- ] -1,5-dioxaspiro [5,5] undecane, and the amount thereof is suitably 1 to 1.2 (mol) relative to the palladium compound.

The carbon monoxide, ethylene and propene are liquid-phase polymerized in a mixed solvent of acetic acid and water to produce a linear terpolymer.

The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone resin is mixed with a layered clay filler and then extruded by an extruder to finally obtain a blend composition. The blend is produced by putting into a twin-screw extruder, melt-kneading and extruding.

In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotational speed is less than 100 rpm, smooth kneading may not occur. If the screw rotation speed is more than 300 rpm, the glass fiber may be broken and the mechanical properties may be deteriorated.

4. Examples and Comparative Examples

Hereinafter, the constitution and effects of the present invention will be described in detail with reference to specific examples and comparative examples, but these examples are merely for the purpose of understanding the present invention more clearly and do not limit the scope of the present invention. The present invention will be described in detail with reference to the following non-limiting examples.

Example 1

Catalysts formed from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) A linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene was prepared in the presence of the composition. 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 46 to 4. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.2 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0.

One part by weight of a silicone resin was mixed with 100 parts by weight of the polyketone terpolymer prepared above, and the mixture was put into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 DEG C and a screw rotation speed of 250 rpm.

Example 2

Catalysts formed from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) A linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene was prepared in the presence of the composition. 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 46 to 4. 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.

One part by weight of a silicone resin was mixed with 100 parts by weight of the polyketone terpolymer prepared above, and the mixture was put into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 DEG C and a screw rotation speed of 250 rpm.

Example 3

Catalysts formed from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) A linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene was prepared in the presence of the composition. 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 46 to 4. 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.

One part by weight of a silicone resin was mixed with 100 parts by weight of the polyketone terpolymer prepared above, and the mixture was put into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 DEG C and a screw rotation speed of 250 rpm.

Example 4

Catalysts formed from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) A linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene was prepared in the presence of the composition. 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 46 to 4. 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 1.8.

One part by weight of a silicone resin was mixed with 100 parts by weight of the polyketone terpolymer prepared above, and the mixture was put into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 DEG C and a screw rotation speed of 250 rpm.

Example 5

Catalysts formed from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) A linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene was prepared in the presence of the composition. 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 46 to 4. 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 2.2.

One part by weight of a silicone resin was mixed with 100 parts by weight of the polyketone terpolymer prepared above, and the mixture was put into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 DEG C and a screw rotation speed of 250 rpm.

Comparative Example

Except that the POM was used as a base material of DuPont, the same procedure as in Example 1 was carried out.

Property evaluation

The prepared pellets of the above Examples were injection-molded to prepare gear specimens usable for ATM. The properties of the gear specimens were evaluated by the following methods in comparison with the products of the comparative examples, and the results are shown in Table 1 below.

1. Product Deformation Rate Evaluation: It was evaluated according to MS211-47 for vertical and horizontal directions at a temperature of 50 DEG C and a relative humidity of 90%.

2. Evaluation of weight change rate of product: Evaluation was made according to MS211-47 under conditions of a temperature of 50 캜 and a relative humidity of 90%.

3. Evaluation of water resistance property retention rate: After 24 hours treatment at 50 ℃ and 90% relative humidity,

4. Evaluation of Wear Rate: The evaluation was made using a cylindrical specimen having an inner diameter of 20 mm, an outer diameter of 25 mm and a height of 15 mm and a counter material. The abrasion loss was measured at a speed of 50 rpm under a JIS K7218 standard, a load of 150 N, and a wear distance of 3 km.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example Product Strain - Vertical
(50 DEG C, 90% RH) 0.05 0.05 0.04 0.05 0.05 0.15 Product Strain - Horizontal
(50 DEG C, 90% RH) 0.02 0.02 0.02 0.02 0.02 0.08 Product weight change rate
(50 DEG C, 90% RH) 0.95 0.85 0.88 0.92 0.94 3.42 Property retention rate
(50 DEG C, 90% RH) 90 88 92 86 88 48 Wear amount
(g) 0.005 0.003 0.004 0.003 0.004 0.083

As shown in Table 1, the deformation rate of the product in the vertical and horizontal directions was lower than that of the comparative example, and the rate of product weight change was also lower than that of the comparative example, and it was excellent in water resistance maintenance and abrasion Respectively.

 In addition, the present invention was superior to the JIS K7218 standard at a speed of 50 rpm, a load of 150 N, a wear distance of 3 km, and a wear amount of 0.020 g or less.

Accordingly, it has been found that the polyketone resin composition prepared through the examples of the present invention can be utilized as an ATM gear or the like which requires excellent abrasion resistance.

Claims (5)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein 0.1 to 15 parts by weight of a silicone resin is contained relative to 100 parts by weight of a polyketone resin having y / x of 0.03 to 0.3,
The ligand of the catalyst composition used in the polymerization of the polyketone is bis (methylene) bis (bis (2-methoxyphenyl) phosphine Pin)
The polyketone resin has an intrinsic viscosity of 1.0 to 2.0 dl / g,
Wherein the silicone resin is in the form of a powder and has a diameter of 1 to 2 占 퐉.
- (CH2CH2-CO) x- (1)
- (CH2CH (CH3) -CO) y- (2)
(x and y are mole% of each of the general formulas (1) and (2) in the polymer)
delete delete The method according to claim 1,
Wherein the polyketone resin has a molecular weight distribution of 1.5 to 2.5.
The method according to claim 1,
Wherein the abrasion resistance of the polyketone resin composition is not more than 0.020 g at a speed of 50 rpm, a load of 150 N, and a wear distance of 3 km under the standard of JIS K7218.