KR101789505B1 - Polyketone resin composition for radiator end tank and a method for manufacturing the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone resin composition for a radiator end tank and a method of manufacturing the same, and more particularly, to a resin composition for automobile radiator end tanks by mixing nylon 6 and nylon MXD6 in a polyketone resin and reinforcing materials such as glass fiber, It is possible to improve the chemical resistance, anti-freeze property, water absorption and durability of the radiator end tank and to save manufacturing cost, and to form an antigelling agent in an alloyed polyketone resin composition such as nylon 6, A polyketone resin composition for a radiator ent tank, and a method for producing the same.

Description

TECHNICAL FIELD The present invention relates to a polyketone resin composition for a radiator end tank, and a method of manufacturing the same.

The present invention relates to a polyketone resin composition that can be used in a radiator end tank and a method of manufacturing the same. More particularly, the present invention relates to a polyketone resin composition for automobile radiator end tanks in which nylon 6 and nylon MXD6 are alloyed with polyketone, To a thermoplastic resin composition which can be used as a component and a method for producing the same using an extrusion process.

The car radiator end tank is located at both ends of the radiator, distributing the antifreeze from the car engine to the radiator core, and the coolant water flowing out of the core. This part is in direct contact with the antifreeze and is in contact with a fluid with a pressure of 1 kg / cm ² and a temperature of 100 ° C or higher. Therefore, the material of the radiator end tank should have pressure resistance and heat resistance.

In addition, automobile radiator end tanks must have mechanical properties that can withstand long-term vibration or shocks caused by running the vehicle, and chemical elements in the external environment such as calcium chloride aqueous solution sprayed on the roads for winter snow removal It should have chemical resistance.

A resin reinforced with nylon 66 / GF33 (polyamide 66) was mainly used as the resin composition satisfying these various characteristics. However, nylon 66 has a low resistance to calcium chloride, which is likely to cause problems in the winter road environment as described above. In order to solve the problem of the nylon 66, a resin reinforced with glass fiber reinforced nylon 612 with nylon 612 and having improved chemical resistance to an aqueous solution of calcium chloride has been used.

It is known that reinforcing nylon 66 by using nylon 612 increases the chemical resistance of calcium chloride. However, the nylon 612 has a problem in that it can not be used in a large amount due to its low heat resistance and high price.

On the other hand, the polyketone resin is a thermoplastic synthetic resin which is excellent in mechanical properties such as impact strength and molding characteristics and is usefully used as a molded article such as a food container and various parts, and its mechanical properties are classified into high performance plastics, A polyketone resin to which other desirable properties such as conductivity are imparted while maintaining inherent physical properties such as molding properties are widely used for various purposes. The polyketone resin has been attracting much attention as an eco-friendly material because it is synthesized from carbon monoxide as a raw material. It is superior to nylon 612 in terms of chemical resistance and has superior price competitiveness compared to other engineering plastics because it uses general monomers such as ethylene and propylene Have.

That is, when the polyketone resin is used as the base resin of the automobile radiator end tank, the cost of the resin consumed will be significantly lower than that of using nylon 66 or nylon 612 resin as the base resin.

However, when a molded article such as an automobile radiator end tank is produced by using a glass fiber composition in which a glass fiber is added to a polyketone resin, gelation easily occurs during molding, resulting in poor workability and a phenomenon of deteriorating the physical properties of the final product frequently do. That is, when glass fibers are added to the polyketone resin, the occurrence of gelation becomes serious, which results in a rough surface. When the molding conditions exceed 260 ° C in extrusion or injection molding, gel generation becomes severe and the color of the product becomes dark.

In order to solve this problem, the present patent has developed a composition to which nylon 6 and MXD6 nylon compositions are controlled in a glass fiber-added composition, and an antigelling agent capable of inhibiting gelation even at high temperatures is added.

Next, a brief description will be given of the prior arts existing in the field to which the technology of the present invention belongs, and the technical matters to be differentiated from the prior arts of the present invention will be described.

Korean Patent Laid-Open Publication No. 2013-0002552 (Mar. 31, 2013) discloses a polyketone resin composition and a method for producing the same. More specifically, the present invention relates to a polyketone resin composition, A technique for improving chemical resistance, anti-freeze-fluid resistance, water absorption, and durability such as calcium chloride resistance is disclosed.

Korean Patent No. 1539680 (Jul. 27, 2015) discloses a heat-radiating composite material composition using a polyketone resin and a molded article thereof. More specifically, the present invention relates to a composite material comprising a polyketone, a graphite, a glass fiber, a processing stabilizer, A description is given of a composition usable as a resin for an automobile radiator end tank manufactured by the method of the present invention.

Korean Patent No. 1675828 (Nov. 19, 2014) discloses a composition technique for improving the mechanical properties of a polyketone composition by adding amorphous semi-aromatic nylon polyhexamethyleneisophthalamide (Nylon 6I) to enhance bending properties have.

The above prior art documents have some similarities with the present invention in that a resin composition for an automobile radiator end tank is produced using polyketone as a base resin. However, as in the present invention, a polyketone resin is used in combination with polymethylaylene adipamide -xylene adipic amide (MXD6)), an artificial rubber composition for improving the physical properties of the resin for the radiator end tank and suppressing the gelation of the resin during molding of the mixed resin composition The present invention differs from the prior art documents in that it is not described.

The present invention provides a resin composition for an automobile radiator end tank by alloying an engineering plastic such as Nylon 6 and MXD6 with a polyketone resin and mixing a reinforcing material and an antigelling agent to provide a resin composition for an automobile radiator end tank which is excellent in chemical resistance, And to improve durability and to improve moldability and manufacturing cost.

A polyketone resin composition for a radiator end tank according to an embodiment of the present invention comprises: 60 to 95 parts by weight of a polyketone resin; 3 to 25 parts by weight of a nylon 6 resin; 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent, wherein the antigelling agent is one obtained by grafting at least one of carboxyl group (-COOH) and acid anhydride group (-C = And is a polymer resin.

In one embodiment, the polyketone resin composition for a radiator end tank further comprises a mineral filler, wherein the content of the mineral filler is 2 to 40 wt% of the total weight of the resin composition.

In one embodiment, the antigelling agent is selected from the group consisting of styrene maleic anhydride resin, styrene / maleimide resin, ethylene resin, propylene resin, ethylene / propylene resin, ethylene / octene resin, ethylene vinyl acetate resin, ethylene / A carboxyl group or an acid anhydride group is grafted onto at least one polymer resin selected from the group consisting of a resin, a styrene / ethylene / butadiene / styrene resin, a polyphenylene oxide, a styrene resin, a styrene / acrylonitrile resin, and an acrylonitrile / butadiene / .

In one embodiment, the mineral filler is at least one selected from the group consisting of glass fiber, mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar and verite.

In one embodiment, the polyketone resin composition for a radiator end tank may have a tensile strength of 147 MPa or more and a flexural strength of 225 MPa or more, preferably a tensile strength of 147 to 160 MPa, 225 to 240 MPa.

According to another embodiment of the present invention, there is provided a method of manufacturing a polyketone resin composition for a radiator end tank, comprising the steps of: (a) mixing nylon 6 resin, nylon MXD6 resin and antigelling agent into a polyketone resin followed by extrusion; And (b) a mineral filler is injected into a side feeder connected to the second half of the extruder in which the extrudate is extruded in step (a), so that the extrudate of step (a) and the mineral filler are mixed together So as to be extruded.

According to another embodiment of the present invention, there is provided a method for manufacturing a polyketone resin composition for a radiator end tank, wherein the polyketone resin composition for a radiator end tank comprises 60 to 95 parts by weight of a polyketone resin, 3 to 6 parts by weight of a nylon 6 resin, 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent, and the content of the mineral filler is 2 to 40% by weight based on the total weight of the total resin composition.

In another embodiment of the present invention, in the method for producing a polyketone resin composition for a radiator end tank of the present invention, the antigelling agent is selected from the group consisting of styrene maleic anhydride resin, styrene / maleimide resin, ethylene resin, , Ethylene / propylene resin, ethylene / octene resin, ethylene vinyl acetate resin, ethylene / propylene / diene resin, styrene / ethylene / butadiene / styrene resin, polyphenylene oxide, styrene resin, styrene / acrylonitrile resin, acrylonitrile / Butadiene / styrene resin is grafted to at least one polymer resin selected from the group consisting of a styrene resin, a butadiene resin, and a styrene resin.

Further, as another embodiment of the present invention, the present invention provides a radiator end tank manufactured using the polyketone resin composition for a radiator end tank described above.

The polyketone resin composition for a radiator end tank according to the present invention comprises a polyketone resin alloyed with nylon 6 and nylon MXD6 and mixed with a reinforcing material such as glass fiber to improve the chemical resistance, anti-freeze property, resistance to water absorption and durability And the manufacturing cost is saved, and an antigelling agent is added, so that the molding can be easily performed at a high temperature.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be construed as limiting of the invention, And the like.

The polyketone resin composition for an automobile radiator end tank according to the present invention comprises: a polyketone resin; Nylon 6 resin; Nylon MXD6 resin; And an antigelling agent, wherein the antigelling agent is a polymer resin in which at least one of a carboxyl group (-COOH) and an acid anhydride group (-C = OOO = C-) is grafted, and the poly The ketone resin composition comprises 60 to 95 parts by weight of a polyketone resin, 3 to 25 parts by weight of a nylon 6 resin, 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent.

The polyketone which is a main component of the polyketone resin composition is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon and contains substantially one carbon monoxide or ketone group per one ethylenically unsaturated hydrocarbon. And has excellent properties and molding properties.

The ethylenically unsaturated hydrocarbon used as a precursor of the polyketone resin is preferably an ethylenically unsaturated hydrocarbon having a carbon number of 20 or less, preferably 10 or less carbon atoms, such as ethene,? -Olefins (e.g., propene, butene, isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons in which an aryl substituent is formed on the aliphatic molecule. The aryl aliphatic hydrocarbon on which the aryl substituent is formed on the aliphatic molecule is an aryl aliphatic hydrocarbon in which an aryl substituent is formed on the ethylenically unsaturated carbon atom. Examples of the aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.

The antigelling agent may be a styrene / maleic anhydride resin, a styrene / maleimide resin, an ethylene resin, a propylene resin, an ethylene / propylene resin, an ethylene / octene resin, an ethylene vinyl acetate resin, an ethylene / propylene / At least one polymer resin selected from the group consisting of ethylene / butadiene / styrene resin, polyphenylene oxide, styrene resin, styrene / acrylonitrile resin, acrylonitrile / butadiene / styrene resin, .

When the carboxyl group or the acid anhydride group molecule is used as the antigelling agent, the mixing property with the polymer resin becomes low. Therefore, the antigelling agent uses a form in which a carboxyl group or an acid anhydride group is grafted to the polymer, Although it is not limited, it is preferable that the polyketone resin, the nylon 6 resin and the nylon MXD6 resin have good mixing properties.

As described above, in the polyketone resin composition for a radiator end tank of the present invention, by incorporating the antigelling agent into the polyketone resin composition for the radiator end tank, the polyketone resin can be easily molded in molding.

 The composition further comprises one or more mineral fillers, wherein the mineral filler content is from 2 to 40% by weight of the total weight of the total resin composition.

The mineral filler may be at least one selected from the group consisting of glass fiber, mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar and verite.

The polyketone resin composition for a radiator end tank according to the present invention may have a tensile strength of 147 MPa or more and a flexural strength of 225 MPa or more by including an antigelling agent in a polyketone resin, a nylon 6 resin, and a nylon MXD6 resin . Preferably, the tensile strength is from 147 to 160 MPa, and the flexural strength is from 225 to 240 MPa.

According to another embodiment of the present invention, there is provided a method of manufacturing a polyketone resin composition for a radiator end tank, comprising the steps of: (a) mixing nylon 6 resin, nylon MXD6 resin and antigelling agent into a polyketone resin followed by extrusion; And (b) a mineral filler is injected into a side feeder connected to the second half of the extruder in which the extrudate is extruded in step (a), so that the extrudate of step (a) and the mineral filler are mixed together So as to be extruded.

As described above, the polyketone resin composition for a radiator end tank according to the present invention is prepared by first mixing a polyketone resin, a nylon 6 resin, a nylon MXD6 resin and an antigelling agent, extruding the mixture with an extruder, .

At this time, the polyketone resin composition for the radiator end tank comprises 60 to 95 parts by weight of a polyketone resin, 3 to 25 parts by weight of a nylon 6 resin, 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent, The content of the mineral filler is preferably 2 to 40% by weight of the total weight of the resin composition.

The antigelling agent is the same as that used for the polyketone resin composition for the radiator end tank.

The present invention also provides a radiator end tank comprising the polyketone resin composition for the radiator end tank.

Hereinafter, the present invention will be described in more detail with reference to examples.

For reference, the following examples are only exemplary embodiments of the present invention, and the present invention is not limited by the following examples.

≪ Examples 1-3 >

Thermoplastic polyketone resin, nylon 6 resin, nylon MXD6 resin, antigelling agent, glass fiber, lubricant and the like were compounded as shown in Table 1 to prepare a polyketone resin composition. The thus-prepared resin composition was melted and extruded in a twin-screw extruder under the conditions of 260 占 폚, L / D = 35, and? = 58 mm to prepare pellets. The pellets thus produced were injection-molded into an ISO family mold at 250 ° C and 500 ton to prepare specimens for the measurement of physical properties.

≪ Comparative Example 1 &

Thermoplastic polyketone resin, antigelling agent, glass fiber, lubricant and the like were compounded as shown in Table 1 to prepare a polyketone resin composition. The thus-prepared resin composition was melted and extruded in a twin-screw extruder under the conditions of 260 占 폚, L / D = 35, and? = 58 mm to prepare pellets. The pellets thus produced were injection-molded into an ISO family mold at 250 ° C and 500 ton to prepare specimens for the measurement of physical properties.

≪ Comparative Examples 2 to 3 >

Thermoplastic polyketone resin, nylon MXD6 resin, antigelling agent, glass fiber, lubricant and the like were compounded as shown in Table 1 to prepare a polyketone resin composition. The thus-prepared resin composition was melted and extruded in a twin-screw extruder under the conditions of 260 占 폚, L / D = 35, and? = 58 mm to prepare pellets. The pellets thus produced were injection-molded into an ISO family mold at 250 ° C and 500 ton to prepare specimens for the measurement of physical properties.

≪ Comparative Example 4 &

Thermoplastic polyketone resin, nylon 6 resin, antigelling agent, glass fiber, lubricant and the like were compounded as shown in Table 1 to prepare a polyketone resin composition. The thus-prepared resin composition was melted and extruded in a twin-screw extruder under the conditions of 260 占 폚, L / D = 35, and? = 58 mm to prepare pellets. The pellets thus produced were injection-molded into an ISO family mold at 250 ° C and 500 ton to prepare specimens for the measurement of physical properties.

≪ Comparative Example 5 &

Thermoplastic polyketone resin, nylon 6 resin, nylon MXD6 resin, glass fiber, lubricant and the like were compounded as shown in Table 1 to prepare a polyketone resin composition. The thus-prepared resin composition was melted and extruded in a twin-screw extruder under the conditions of 260 占 폚, L / D = 35, and? = 58 mm to prepare pellets. The pellets thus produced were injection-molded into an ISO family mold at 250 ° C and 500 ton to prepare specimens for the measurement of physical properties.

For reference, in the above Examples 1 to 3 and Comparative Examples 1 to 4, M330A (manufactured by Hyosung Corporation) having a melting point of 220 DEG C and a flowability of 260 g / 10 min at 240 DEG C and 2.16 kg was used as the thermoplastic polyketone resin , Toplan 1101 (manufactured by Hyosung) as the nylon 6 resin, MXD6 of MXD6 of Mitsubishi Gas Chemical of Japan, and SPO2 of Hyundai Pisa, which is a polyphenylene oxide having an acid anhydride group as an antigelling agent. As the lubricant, Licowax E from Clariant was used. Other additives added to other resin compositions were used which were readily available commercially.

Content (parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyketone resin 87 80 70 100 90 80 70 80 Nylon 6 10 10 10 - - - 30 10 Nylon MXD6 3 10 20 - 10 20 - 10 Antigelling agent One One One One One One One - Lubricant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Glass fiber,% 33 33 33 33 33 33 33 33

Test 1: Measurement of tensile strength, flexural strength and heat distortion temperature

Tensile strength, flexural strength and HDT heat distortion temperature of the compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured, and the measurement method was as follows.

(1) Tensile strength (unit: MPa): The tensile strength was measured by the ISO 527 method.

(2) Flexural strength (unit: MPa): Flexural strength was measured by the ISO 178 method.

(3) Heat deformation temperature (unit: ° C): Measured under the load condition of 1.8 MPa by the ISO 75-1,2 method.

Test 1 Results

Table 2 below shows the tensile strength, flexural strength and HDT heat distortion temperature of the compositions of the compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 importance 1.47 1.47 1.48 1.48 1.47 1.46 1.45 1.47 Tensile strength, MPa 149 157 154 140 140 142 145 130 Flexural Strength, MPa 227 235 230 220 217 220 222 170 Heat distortion temperature, ℃ 215 217 216 214 217 216 217 213

As shown in Table 2, the compositions (Examples 1 to 3) prepared by blending nylon 6 resin and nylon MXD6 resin in a polyketone resin (Comparative Example 1) and polyketone The tensile strength and the flexural strength were measured to be higher than the compositions (Comparative Examples 2 to 4) containing only nylon MXD6 resin or nylon 6 resin in the resin.

In addition, in the results of measuring the heat distortion temperature showing heat resistance, the compositions (Examples 1 to 3 and Comparative Examples 2 to 4) containing nylon 6 resin or nylon MXD6 resin in comparison with the composition prepared only with polyketone resin (Comparative Example 1) ) Were measured to have heat resistance up to a higher temperature.

In addition, the results of Examples 1 to 3 show the best properties in the composition (Example 2) prepared by blending 80 parts by weight of polyketone resin, 10 parts by weight of nylon 6 resin and 10 parts by weight of nylon MXD6 resin.

In the case of Comparative Example 5, in the case where the antigelling agent according to the present invention was not added, the bending strength and tensile strength of the gel produced during molding were considerably lower than those of the other examples, and the workability was also poor.

Test 2: Durability measurement

As a polyketone composition according to the present invention, a radiator tank was molded from the pellets prepared in the composition of Example 2 and the pellets prepared in the composition of Comparative Example 1 for comparison with the radiator tank, and after mounting the radiator tank to the radiator, Durability test was performed.

The test was conducted under the condition that the antifreeze was circulated at a cycle of 1 Hz at a pressure of 1.5 kgf / cm 2 under an antifreeze temperature condition of 123 ° C, and the portion mounted on the radiator was vibrated at a predetermined period.

Test 2 Results

Table 3 below shows the durability measurement results according to Test 2. The formulation of Example 3 showed the results of the composite vibration endurance passing the standard.

Example 2 Comparative Example 1 Composite vibration endurance cycle Over 100,000 35,000

As shown in Table 3, the radiator tank made of the composition (Example 2) prepared by blending nylon 6 resin and nylon MXD6 resin into the polyketone resin was superior to the composition (Comparative Example 1) made only of polyketone resin The composite vibration durability was significantly higher than the standard durability required for the radiator tank.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the technical scope of the present invention should be determined by the following claims

Claims (9)

A polyketone resin composition for a radiator end tank,
60 to 95 parts by weight of a polyketone resin; 3 to 25 parts by weight of a nylon 6 resin; 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent,
Wherein the antigelling agent is a polymer resin in which at least one of a carboxyl group (-COOH) and an acid anhydride group (-C = OOO = C-) is grafted. The method according to claim 1,
Wherein the polyketone resin composition for the radiator end tank further comprises at least one mineral filler,
Wherein the content of the mineral filler is 2 to 40 wt% of the total weight of the total resin composition. The method according to claim 1,
The antigelling agent is selected from the group consisting of styrene maleic anhydride resin, styrene / maleimide resin, ethylene resin, propylene resin, ethylene / propylene resin, ethylene / octene resin, ethylene vinyl acetate resin, ethylene / propylene / Wherein at least one polymer resin selected from the group consisting of acrylonitrile / butadiene / styrene resin, polyphenylene oxide, styrene resin, styrene / acrylonitrile resin and acrylonitrile / butadiene / styrene resin is grafted with a carboxyl group or an acid anhydride group. Polyketone resin composition for end tanks. 3. The method of claim 2,
Wherein the mineral filler is at least one selected from the group consisting of glass fiber, mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar and verite. The method according to claim 1,
Wherein the polyketone resin composition for a radiator end tank has a tensile strength of 147 MPa or more and a flexural strength of 225 MPa or more. A method for producing a polyketone resin composition for a radiator end tank,
(a) mixing polyketone resin with nylon 6 resin, nylon MXD6 resin and antigelling agent, and extruding the mixture; And
(b) a mineral filler is introduced into a side feeder connected to the second half of the extruder to which the extrudate is extruded in step (a), and the extrudate of step (a) and mineral filler are mixed together, Wherein the polyketone resin composition is a polyketone resin composition for a radiator end tank. The method of claim 6, wherein
Wherein the polyketone resin composition for the radiator end tank comprises 60 to 95 parts by weight of a polyketone resin, 3 to 25 parts by weight of a nylon 6 resin, 1 to 30 parts by weight of a nylon MXD6 resin and 0.2 to 2 parts by weight of an antigelling agent,
Wherein the content of the mineral filler is 2 to 40% by weight of the total weight of the resin composition. The method according to claim 6,
The antigelling agent is selected from the group consisting of styrene maleic anhydride resin, styrene / maleimide resin, ethylene resin, propylene resin, ethylene / propylene resin, ethylene / octene resin, ethylene vinyl acetate resin, ethylene / propylene / Wherein a carboxyl group or an acid anhydride group is grafted onto at least one polymer resin selected from the group consisting of styrene / butadiene / styrene resin, polyphenylene oxide, styrene resin, styrene / acrylonitrile resin, acrylonitrile / butadiene / styrene resin. Wherein the polyketone resin composition is a polyketone resin composition. A radiator end tank manufactured using the polyketone resin composition for a radiator end tank according to any one of claims 1 to 5.