KR20160059901A - Polyketone blend for radiator end tank of vehicle - Google Patents

Abstract

The present invention relates to a radiator end tank of vehicles, which is produced by injection-molding a blend of linear alternating polyketone consisting of carbon monoxide and at least one ethylene-based unsaturated hydrocarbon, glass fibers, nylon 6I, and a silane additive. The radiator end tank of vehicles has high physical property maintenance rate after absorbing water, excellent water resistance, and excellent chemical resistance.

Description

Technical Field [0001] The present invention relates to a polyketone resin composition for a radiator end tank of an automobile,

The present invention relates to a polyketone resin composition which can be used as a material for a radiator end tank of an automobile, and more particularly, to a polyketone resin composition which can be used as a material for a radiator end tank of an automobile, and more particularly to a polyketone resin composition which is composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, And an automobile radiator end tank obtained by injection molding a blend.

Polyamide 66 resin, one of the thermoplastic engineering plastics, is used as a material for radiator end tanks in the automotive industry because of its excellent heat resistance and impact resistance. The radiator end tank made of polyamide 66 material has high heat resistance and impact resistance that can withstand the heat of engine. It is not only resistant to high heat and vibration due to long time operation of automobile but also excellent in production. Level. However, due to the dimensional change and physical property degradation caused by moisture absorption of nylon material, the product abnormality such as appearance abnormality or inability to detach from the Fill Filler Door during use after assembling the automobile was limited in designing various products.

On the other hand, the polyamide 66 resin is not so large in weight per product, but it is difficult to separate the inserted iron, copper, and rubber materials, so it is buried under ground or burned. It is also a cause.

In order to solve the above problems, Korean Patent Laid-Open Publication No. 10-2012-0005254 discloses a method for producing a recycled polyamide 66 resin. This document discloses a method of manufacturing a pulverized radiator end tanks, comprising: pulverizing a spent radiator end tank and a waste engine cover; Washing the pulverized material with an aqueous solution of microbial detergent; Mixing the cleaned material with 45 to 55 wt% of the waste radiator end tank material and 45 to 55 wt% of the waste engine cover material to produce a mixture; And a step of melting and extruding the mixture and the chain extender to pelletize the polyamide 66 resin.

This makes it possible to produce recycled polyamide 66 resin with high added value and excellent mechanical properties, and the recycled resin can be recycled to expect the cost reduction effect and the environmental pollution problem due to incineration or landfill can be prevented.

However, since the same polyamide resin is used only as a method of recycling the waste radiator end-tank resin composition, the above document completely solves the disadvantages of being susceptible to the dimensional changes due to moisture absorption, changes in physical properties, impact resistance and chemical resistance I can not.

Korean Patent No. 1006685720000 Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

DISCLOSURE OF THE INVENTION In order to solve the above problems, the present invention provides a polyketone composition for an automobile radiator end tank having excellent physical property retention and excellent impact resistance and chemical resistance by using a polyketone blend comprising a polyketone copolymer and a mineral filler The purpose is to provide.

In order to solve the above problems, the present invention provides a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein the polyketone copolymer has a y / x of 0.03 to 0.3; Glass fiber; Nylon 6I; Of silane additives; The present invention provides a polyketone resin composition for use in an automobile radiator end tank, which is produced by injection molding a blend.

- (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)

Wherein the polyketone copolymer has an intrinsic viscosity of 1.0 to 2.0 dl / g and a molecular weight distribution of 1.5 to 2.5, and the polyketone copolymer; Glass fiber; Nylon 6I; The silane additive is mixed in an amount of 50 to 80% by weight, 20 to 40% by weight, 5 to 20% by weight and 0.1 to 10% by weight, respectively, based on the weight ratio.

On the other hand, the polyketone resin composition of the present invention has a property retention ratio of 80% or more when evaluated by ME / ES SPEC (MS211-47) under conditions of a fuel temperature of 50 캜 and a relative humidity of 90%, a temperature of 50 캜 and a relative humidity of 90% Under the condition of ME / ES SPEC (MS211-47), the product weight change ratio is 5.0% or less.

The automotive radiator end tank of the present invention comprises a polyketone copolymer and glass fibers; Nylon 6I; It is composed of silane additive, which has higher water retention after water absorption than conventional polyimide 66, and has excellent water resistance and chemical resistance.

Hereinafter, the present invention will be described in detail.

1. Polyketone polymer

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 polymer 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) 1,3-bis [di (2-methoxyphenyl) phosphino] propane.

 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, tricyclo undecene, 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.

2. Fiberglass

In the present invention, glass fibers are added to improve the deformation rate and physical property retention of the above-mentioned alternating polyketone. The amount of the glass fiber to be added may be 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 33% by weight based on 50 to 74.9% by weight of the polyketone copolymer. If it does not reach 20 wt%, deformation of the product after moisture absorption is severe and it is difficult to maintain the physical properties. If it exceeds 40 wt%, there arises a problem in mechanical processing such as molding.

3. Nylon 6I

In the present invention, in order to enhance the heat resistance of the linear alternating polyketone, nylon 6I is mixed to prepare a polyketone resin composition. The amount of nylon 6I added is 5 to 20% by weight based on 50 to 74.9% by weight of the polyketone copolymer desirable. If it does not reach 5 wt%, the heat resistance is not excellent. If it exceeds 20 wt%, the inherent impact resistance and abrasion resistance of the polyketone deteriorate. The preferable content is 10% by weight relative to 50 to 74.9% by weight of the polyketone copolymer.

4. Silane Additive

In the present invention, a silane additive is added to enhance the mechanical properties such as impact resistance of the above-mentioned alternating polyketone. The silane additive is preferably added in an amount of 0.1 to 10% by weight based on 50 to 74.9% by weight of the polyketone copolymer. If it does not reach 0.1 wt%, the mechanical properties are not good, and if it exceeds 10 wt%, the mechanical properties do not improve any more. The most preferable addition amount is 0.3% by weight relative to 70 to 80% by weight of the polyketone copolymer.

5. Manufacturing Method

Hereinafter, a method of manufacturing the polyketone blended automobile radiator end tank as described above will be described.

A method for producing a polyketone blended automobile radiator end tank 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 (for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane and 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, the amount of which is 1 to 1.2 ) Equivalent.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of 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, glass fiber, nylon 6I and silane additives are added to the obtained polyketone resin

Mixed and extruded with 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.

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

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

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 with HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and the MI index was 48 g / 10 min. 56.7% by weight of the polyketone terpolymer prepared above, 33% by weight of glass fiber, 10% by weight of nylon 6I and 0.3% by weight of a silane additive were mixed and put into an extruder. The extruder was operated at 250 rpm and had a diameter of 2.5 cm. Was prepared in the form of pellets on an extruder using a biaxial screw.

Comparative Example

33% by weight of glass fiber was used as a material of DuPont in comparison with 100% by weight of a polyimide resin mixed with 70% by weight of polyamide 66 (PA 66) and 30% by weight of polyimide 612 (PA 612) A specimen was prepared for the mixed polyimide resin composition.

Property evaluation

The prepared pellets of the above examples were injection-molded to prepare automotive radiator end tank specimens. The specimens were evaluated in the following manner in comparison with the specimens of the comparative examples. 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. Antifreeze evaluation: Evaluation at 146 占 폚 for 144 hours

5. Evaluation of oil resistance: Antifreeze and Mission Oil were mixed and evaluated at 120 ° C. for 144 hours

6. Evaluation of heat aging: 10% aqueous calcium chloride solution, evaluation at 120 ° C for 144 hours

Item Example Comparative Example Product Strain Rate Evaluation (Vertical, 50 ℃, Relative Humidity 90%) 0.05% 0.30% Evaluation of product strain (horizontal, 50 ℃, relative humidity 90%) 0.02% 0.25% Product weight change rate (50 ℃, relative humidity 90%) 0.95% 6.50% Water resistance Property retention rate (50 ℃, relative humidity 90%) 90% 50% My anti-freeze property 71% 38% Oil resistance 86% 59% Heat aging resistance 85% 61%

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.

 Particularly, the specimen of the polyketone resin composition was evaluated by ME / ES SPEC (MS211-47) under conditions of a fuel temperature of 50 ° C and a relative humidity of 90%, and a retention ratio of properties such as antifreeze property, oil resistance, Respectively.

Also, the product weight change rate was superior to 5.0% in ME / ES SPEC (MS211-47) at 50 ℃ and 90% relative humidity.

Therefore, the automobile radiator end tank manufactured through the embodiment of the present invention proved to be very suitable for use as an automobile radiator end tank because the fuel is excellent in water resistance, dimensional stability, and chemical resistance.

Claims (5)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein the polyketone copolymer has a y / x of 0.03 to 0.3; Glass fiber; Nylon 6I; Of silane additives; Wherein the polyketone resin composition is produced by injection molding a blend.

- (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 polyketone copolymer has an intrinsic viscosity of 1.0 to 2.0 dl / g and a molecular weight distribution of 1.5 to 2.5.
The method according to claim 1,
Said polyketone copolymer; Glass fiber; Nylon 6I; Wherein the silane additive is mixed in an amount of 50 to 74.9% by weight, 20 to 40% by weight, 5 to 20% by weight and 0.1 to 10% by weight based on the weight ratio, respectively.
The method according to claim 1,
Wherein the polyketone resin composition has a physical property retention ratio of 80% or more when evaluated by ME / ES SPEC (MS211-47) under conditions of a fuel temperature of 50 캜 and a relative humidity of 90%. The polyketone resin used in an automobile radiator end tank Composition.
The method according to claim 1,
Wherein the polyketone resin composition has a product weight change rate of 5.0% or less when evaluated by ME / ES SPEC (MS211-47) under the conditions of a temperature of 50 캜 and a relative humidity of 90%. The polyketone resin used in an automobile radiator end tank Composition.