KR101664250B1 - Polyketone blend Fuel Filler Door - Google Patents

Abstract

The present invention relates to an automotive fuel injection port manufactured by injection molding a blend of a linear alternating polyketone and a mineral filler composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon. More particularly, The present invention relates to a blended automobile fuel injection port.

Description

{Polyketone blend Fuel Filler Door}

The present invention relates to an automobile fuel inlet using a polyketone blend, and more particularly, to an automobile fuel inlet obtained by injection molding a blend of a linear alternating polyketone and a mineral filler composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon.

Conventional automotive fuel filler door parts are mostly made of nylon

We used 10 ~ 40% of inorganic filler.

Particularly, there is a problem in that a conductive primer is applied after component injection to use parts coated with in-line painting in the assembly line of a finished car, which causes an excessive process cost. In addition, due to dimensional changes and deterioration of physical properties due to moisture absorption of nylon material, there were limitations in designing various products, such as appearance abnormality and inability to detach from the Fill Filler Door during use after assembling the automobile.

Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

In order to solve the above-mentioned problems, the present invention aims to obtain an automobile fuel inlet which is characterized by sufficient water resistance, chemical resistance and dimensional stability by using a polyketone blend comprising a polyketone copolymer and a mineral filler.

In order to achieve the above technical object, there is provided a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein a blend of a polyketone copolymer having y / x of 0.03 to 0.3 and a mineral filler The present invention provides a polyketone blended automobile fuel inlet which is manufactured by injection molding.

- (CH2CH2-CO) x- General formula (1)

- (CH2CH (CH3) -CO) y- < / RTI >

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

Also, the fuel injection port has a product weight change rate of 2.5% or less when evaluated by ME / ES SPEC (MS211-47) under conditions of a temperature of 50 캜 and a relative humidity of 90%.

Further, the rate of change in the vertical direction or the horizontal direction is 0.12% or less when the fuel injection port is evaluated by ME / ES SPEC (MS211-47) at a temperature of 50 캜 and a relative humidity of 90%. The polyketone blend vehicle Thereby providing a fuel inlet.

The mineral filler may be selected from the group consisting of Talc, Kaolin, Mica, wollastonite, TiO2-coated mica platelets, silica, alumina alumina, borosilicates, and oxides. The present invention also provides an automotive fuel injection port.

In addition, the present invention provides an automotive fuel injection port, wherein the mineral filler is 5 to 50 wt% based on 100 wt% of the blend.

Since the automobile fuel injection port of the present invention includes the polyketone copolymer and the mineral filler, the effect of maintaining the physical properties after moisture absorption is higher than that of the conventional nylon blend. Therefore, it is possible to obtain an automobile fuel injection port improved in water resistance, chemical resistance and dimensional stability by injection molding a polyketone blend.

Hereinafter, the present invention will be described in detail.

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. (2-methoxyphenylphosphino)] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine), and the amount of use is preferably 1 to 1.2 equivalents relative to palladium.

2. Polyketone polymerization process

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.

Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.

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, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, 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 copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

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

 Examples of the ligands (b) having an atom of Group XIII include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) (2-methoxyphenyl) propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine] propane, (Diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) (Diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxy- (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2- Spinosyns; there may be mentioned a ligand, such as propane.

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 preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).

(2)

.

.

      Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5- 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) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per 1 liter 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.

 Wherein the carbon monoxide and the ethylenically unsaturated compound and the propylenically unsaturated compound are copolymerized with an organometallic complex comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) or group 15 Catalyzed, 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.

3. Mineral filler

In the present invention, the above-mentioned mineral filler is a mixture of talc, kaolin, mica, wollastonite, TiO 2 -coated, TiO 2 -coated mica platelets, silica, alumina, borosilicates, and oxides.

The content of the mineral filler is 5 to 50% by weight. And preferably 30 to 40% by weight. When the mineral filler is added in an amount of less than 5% by weight, dimensional stability is deteriorated. When the mineral filler is more than 50% by weight, the injection moldability is inferior.

4. Manufacturing Method

Hereinafter, a method for manufacturing the polyketone blended automobile fuel injection port as described above will be described.

A method for producing a polyketone blended automobile fuel inlet of the present invention comprises the steps of: 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 an alcohol (for example, methanol) 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 propylene; 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.

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino)] propane, Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) may be used, and the amount thereof is suitably 1 to 1.2 (mol) relative to the palladium compound.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed 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 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 mineral 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 rotating speed is less than 100 rpm, smooth kneading may not occur and mechanical properties may be deteriorated.

A polyketone blended automobile fuel inlet can be manufactured by preparing a blend and injecting it by the same method as described above.

5. 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. However, these examples are merely intended to clearly understand the present invention and are not intended to 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

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). 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, and the MI index was 60 g / 10 min. 70 weight% of the polyketone terpolymer prepared above and 30 weight% of mineral filler were pelletized on an extruder using a twin screw having a diameter of 40 mm and operating at 250 rpm and having L / D = 32, To prepare specimens for fuel injection holes.

Example 2

The same as Example 1 except that 80 wt% of polyketone terpolymer and 20 wt% of mineral filler were used.

Example 3

The same as Example 1 except that 90 wt% of the polyketone terpolymer and 10 wt% of the mineral filler were used.

Comparative Example 1

The moisture retention after moisture absorption of 60 wt% of polyamide 66 (PA 66) and 40 wt% of mineral filler was measured as a material of DuPont.

Property evaluation

The prepared pellets of the above examples were injection-molded to prepare test specimens for an automobile fuel injection port. The test specimens were evaluated in the following manner in comparison with the products of the comparative examples, and the results are shown in Table 1 below.

1. Strain rate evaluation: Evaluation was made 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: Evaluation was made according to MS211-47 at a temperature of 50 占 폚 and a relative humidity of 90%.

3. Evaluation of water resistance retention: Mechanical properties were evaluated by ME / ES SPEC (MS211-47) after treatment at a temperature of 50 ° C and a relative humidity of 90% for 500 hours.

Item unit Comparative Example 1 Example 1 Example 2 Example 3  Strain rate evaluation (vertical, 50 캜, relative humidity 90%) % 0.3 0.05 0.07 0.10  Strain rate evaluation (horizontal, 50 ℃, relative humidity 90%) % 0.25 0.02 0.04 0.07  Weight change rate (50 캜, relative humidity 90%) % 6.5 0.95 1.00 1.95 Water resistance Property retention (tensile strength, 50 ℃, relative humidity 90%) MPa 39 63 59 56 Water resistance Property retention (Flexural strength, 50 ℃, Relative humidity 90%) MPa 65 95 96 97 Water Resistance Property retention (Flexural modulus, 50 ℃, Relative humidity 90%) MPa 1980 2310 2320 2360 Water resistance Property retention (impact strength, 50 ℃, relative humidity 90%) KJ / m ² 6.4 7.1 8.0 8.3

As shown in Table 1, in the case of the examples, the strain rate was lower in the evaluation of the product strain rate in the vertical direction and the horizontal direction than the comparative example, and the product weight change rate was also lower than that of the comparative example, It was evaluated as excellent. Therefore, the automobile fuel injection port manufactured through the embodiment of the present invention is excellent in water resistance and dimensional stability, and thus is well suited for application as an automobile fuel injection port.

Claims (6)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), which is produced by injection molding a blend of a polyketone copolymer and a mineral filler having a ratio y / x of 0.03 to 0.3,
The mineral filler may be selected from the group consisting of Talc, Kaolin, Mica, wollastonite, TiO2-coated mica platelets, silica, alumina, Borosilicates, and oxides, and is preferably selected from the group consisting of oxides,
Based on 100% by weight of the total blend, the mineral filler is 5 to 50% by weight,
The polyketone has an intrinsic viscosity of 1.0 to 2.0 dl / g, and the ligand of the catalyst composition used in the polymerization of the polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine)
Wherein the rate of change in the vertical direction or the horizontal direction is 0.12% or less at a temperature of 50 캜 and a relative humidity of 90%.
- (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 method according to claim 1,
Wherein the automobile fuel inlet has a flexural strength of 80 MPa or more at a temperature of 50 캜 and a relative humidity of 90%.
The method according to claim 1,
Wherein the automobile fuel inlet has a weight change ratio of 2.5% or less under conditions of a temperature of 50 캜 and a relative humidity of 90%.
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