KR102575162B1 - Theromplastic resin composition for air intake hose and air intake hose using the same - Google Patents

Abstract

The present invention relates to a heat-resistant resin composition for an air intake hose, and more specifically, includes a heat-resistant impact block copolymer, ethylene propylene rubber grafted with maleic anhydride, polyester-based elastomer, inorganic reinforcement, heat-resistant stabilizer, antioxidant, and lubricant. The present invention relates to a heat-resistant resin composition for an air intake hose that has excellent heat-resistant properties as well as durability and lightweight properties through the development of a composition that provides heat-resistant properties.

Description

Thermoplastic resin composition for air intake hose and air intake hose using the same {THEROMPLASTIC RESIN COMPOSITION FOR AIR INTAKE HOSE AND AIR INTAKE HOSE USING THE SAME}

The present invention relates to a thermoplastic resin composition for an air intake hose, and more specifically, includes a heat-resistant impact block copolymer, ethylene propylene rubber grafted with maleic anhydride, polyester-based elastomer, inorganic reinforcement, heat-resistant stabilizer, antioxidant, and lubricant. The present invention relates to a thermoplastic resin composition for an air intake hose that is excellent in heat resistance as well as durability, lightness, and heat resistance through the development of a composition, and an air intake hose using the same.

The air intake hose mounted on a car sends air sucked in from the outside of the vehicle to the air cleaner or sends air filtered from the air cleaner to the throttle body of the car engine. ) and is a part installed in the vehicle engine room that forms a passage for air to flow between the engine and the air cleaner.

As shown in FIG. 1, the air intake hose that is conventionally applied includes an engine connection portion 110 connected to the engine, an air cleaner connection portion 130 connected to an air cleaner, and the engine connection portion 110 and air cleaner connection portion 130. ) and consists of a bellows (120) connecting it.

The engine connection part 110 is made of a material containing ethylene-methyl acrylate (AEM), which has heat resistance to high temperatures of 170°C or higher transmitted from the engine, and is relatively maintained at a constant temperature of about 130°C. A material containing epichlorohydrin rubber (ECO) is used in the air cleaner connection part 130, through which lower-temperature air passes than the engine connection part 110, and the engine connection part made of this material in the bellows 120 Since 110 and the air cleaner connection portion 130 are connected to each other using a ring-shaped clamp 140, such a conventional air intake hose has a problem in that its overall weight and specific gravity are high. Therefore, there is a need for technology to improve this and make it lighter.

Republic of Korea Patent Publication No. 10-1527025

The present invention was developed to improve the problems described above. Polypropylene, a rigid and heat-resistant impact block copolymer with excellent heat resistance and mechanical strength, is used to reduce the weight of the air cleaner connection, and is modified for low-temperature impact resistance. Rubber grafted with functional compounds to rubber, polyester-based elastomer to reduce costs, kaolin-based plate-shaped inorganic material to ensure thermal and dimensional stability, phenolics and phosphorus-based (Phosphites) An air intake with excellent heat resistance as well as durability and lightness by composing a composition containing an antioxidant and an olefin-based lubricant and applying a rubber heat-resistant stabilizer to suppress the volatility of the rubber component at high temperatures as an additional function. The purpose is to provide a thermoplastic resin composition for hoses and an air intake hose manufactured using the same.

The thermoplastic resin composition for an air intake hose of the present invention to achieve the above object includes polypropylene-based impact block copolymer, maleic anhydride-grafted ethylene propylene rubber (EPDM), polyester-based elastomer, and inorganic materials. It may include reinforcing materials, heat stabilizers, antioxidants, and olefin-based lubricants.

Specifically, the content of each component in the thermoplastic resin composition for the air intake hose is 20 to 30% by weight of the polypropylene-based impact block copolymer and 50 to 60% by weight of the maleic anhydride-grafted ethylene propylene rubber (EPDM). % by weight, 10 to 20% by weight of the polyester-based elastomer, 5 to 10% by weight of the inorganic reinforcing material, 1 to 3% by weight of the heat stabilizer, 0.3 to 0.5% by weight of the antioxidant, and 0.2 to 0.5% by weight of the olefin-based lubricant. It can be included.

Polypropylene, an impact block copolymer used as a resin raw material for thermoplastic resin compositions for air intake hoses, is a resin for reducing the weight of air intake hoses and is a resin raw material with excellent mechanical rigidity and heat resistance during the blow molding process of the composition. am.

The maleic anhydride-grafted ethylene propylene rubber (hereinafter also referred to as 'MA-g EPDM') used as a rubber raw material is compatible with the resin raw material and kaolin, an inorganic reinforcing material added to ensure dimensional stability. Ethylene propylene rubber (EPDM), a rubber raw material used to improve impact resistance by ensuring compatibility, has excellent heat resistance and is a copolymerization of ethylene, propylene, and non-conjugated diolefin. It is a rubber modified by grafting maleic anhydride with a functional compound to improve impact resistance.

Additionally, as a rubber raw material, polyester-based elastomer can be used along with ethylene propylene rubber (MA-g EPDM) grafted with maleic anhydride.

The polyester-based elastomer is a relatively cheaper rubber raw material than the maleic anhydride-grafted ethylene propylene rubber, and the content of the maleic anhydride-grafted ethylene propylene rubber (MA-g EPDM) used in all rubber raw materials is reduced, It is economical by reducing costs, and the impact strength of the composition can be improved by using a high-impact polyester-based elastomer with a shore hardness of 35 to 45D.

The inorganic reinforcing material is preferably plate-shaped kaolin to secure heat resistance at high temperatures and improve impact resistance and dimensional stability.

If the inorganic reinforcing material containing plate-shaped kaolin is less than 5% by weight in the thermoplastic resin composition for air intake hose, dimensional stability is reduced, causing post-deformation problems, and conversely, if the inorganic reinforcing material is added in excess of 10% by weight, molding Since the problem of deterioration of processability occurs, the inorganic reinforcing material containing plate-shaped kaolin is preferably included in an amount of 5 to 10% by weight.

The heat-resistant stabilizer is a component for improving the long-term heat resistance of the air intake hose by suppressing the volatility of the rubber component at high temperatures. For example, an amine-based heat-resistant stabilizer, a phenolic-based heat-resistant stabilizer, a monophenol-based heat-resistant stabilizer, a bisphenol-based heat-resistant stabilizer, Polymer-type phenol-based heat-resistant stabilizers, thiol-based heat-resistant stabilizers, phosphorus-based heat-resistant stabilizers, etc. can be used, but are not limited to these and ordinary heat-resistant stabilizers for rubber can be used.

If the heat-resistant stabilizer in the thermoplastic resin composition for air intake hose is less than 1.0% by weight, the content is so small that heat aging resistance is reduced. Conversely, if it exceeds 3.0% by weight, heat resistance may decrease and problems may occur in the appearance quality of the molded product. It is preferable that the heat-resistant stabilizer is included in an amount of 1 to 3% by weight.

The antioxidant may be one or more selected from phenol-based antioxidants and phosphorus-based antioxidants as an ingredient to suppress oxidative degradation during the subsequent molding process.

The phenol-based antioxidant is tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ]methane), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)(1,3,5-Trimethyl-2,4 ,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), 1,6-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido ]hexane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane), 1,6-bis[3-(3,5-di-tert-butyl- One or more selected from 4-hydroxyphenyl)propionamido]propane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane) can be used.

The phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)pentaerythritol-di-phosphite (Tris(2,4-di-t-butylphenyl)-phosphite) and bis(2,6- Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite) and bis(2,4-di- Any one or more selected from Bis(2,4-di-tert-butylphenyl)pentraerythritol-di-phosphite can be used.

It is not limited to the phenol-based antioxidants and phosphorus-based antioxidants presented above, and phenolic antioxidants and phosphorus-based antioxidants that can be easily practiced by those skilled in the art to which the present invention pertains can be applied and used.

If the amount of the antioxidant in the thermoplastic resin composition for air intake hose is less than 0.3% by weight, the oxidative deterioration reaction cannot be suppressed, causing a problem of deterioration in the long-term stability and durability of the molded product, and if it exceeds 0.5% by weight, the thermoplastic resin composition manufactured with this thermoplastic resin composition Since the problem of deterioration in the appearance quality of the molded product occurs, it is preferable that the antioxidant is included in an amount of 0.3 to 0.5% by weight.

Olefin-based lubricants can further improve moldability by improving the fluidity and release properties of the thermoplastic resin composition for intake hoses.

The olefin-based lubricant may be included in an amount of 0.2 to 0.5% by weight based on the total composition of the thermoplastic resin composition for an intake hose. If the olefin-based fume content is less than 0.2% by weight, the fluidity and release properties are lowered, which reduces the processability of the thermoplastic resin composition for the intake hose. If it exceeds 0.5% by weight, the molding processability is lowered and the fusion strength is lowered. Therefore, it is desirable to satisfy the content range presented above.

In addition, in order to improve the color stability of the thermoplastic resin composition for the air intake hose, carbon black may be further included, and the carbon black is not limited as long as it is ordinary carbon black well known in the art, For example, one or more selected from ketjen black, acetylene black, furnace black, and channel black can be used.

The carbon black of the present invention is preferably used in the form of a master batch in order to further improve molding processability and color stability by improving the dispersibility of carbon black in the thermoplastic resin composition for air intake hoses.

The content of carbon black according to an embodiment of the present invention may be 1 to 2% by weight based on the total thermoplastic resin composition for air intake hose. If the content of carbon black exceeds 2% by weight, molding processability and Since physical properties of color stability may be deteriorated, it is desirable to satisfy the content range presented above.

The thermoplastic resin composition for an air intake hose having the composition described above can be manufactured by a general method used in the art, and the method is not particularly limited.

As described above, an automobile air intake hose can be manufactured using the thermoplastic resin composition for an air intake hose of the present invention.

The thermoplastic resin composition for air intake of the present invention as described above is used in place of the ECO material applied to the air cleaner connection part connected to the air cleaner of the conventional air intake hose in order to reduce the weight of the air intake and further improve the mechanical rigidity properties. Polypropylene, a rigid and heat-resistant impact block copolymer with excellent heat resistance and mechanical strength, rubber grafted with functional compounds to rubber modified for low-temperature impact resistance, and cost reduction By using a composition containing polyester-based elastomer and kaolin-based plate-shaped minerals to ensure thermal and dimensional stability, heat resistance and weight reduction can be balanced, and functional additives such as heat stabilizers and antioxidants can be added. This function has the effect of improving physical properties such as impact and long-term heat resistance.

In addition, cost reduction effects can be expected due to the composition of resin and rubber raw materials that are relatively cheaper than conventional ECO materials.

Figure 1 is a simplified schematic diagram of a conventional air intake hose.
Figure 2 is an exemplary diagram of an air intake hose according to an embodiment of the present invention.

Terms such as “consists,” “includes,” or “added” used in the specification should not be construed as necessarily including all of the various components described in the specification, and some of the components may not be included. It can also be interpreted as being able to include additional components.

Hereinafter, examples and comparative examples of the thermoplastic resin composition for an air intake hose of the present invention will be described in detail. These examples and comparative examples are examples and can be used in various different forms by those skilled in the art to which the present invention pertains. Since it can be implemented, it is not limited to the embodiment described herein.

Thermoplastic resin compositions for air intake hoses according to Comparative Examples 1 to 6, Examples 1 and 2 were prepared by uniformly mixing the ingredients and contents shown in Table 1 below.

In Table 1 below, polypropylene is B310 from Lotte Advanced Materials, ECO is epichlorohydrin rubber, and maleic anhydride grafted ethylene propylene rubber (MA-g EPDM) is KEPA 1130 from Kumho Petrochemical and polyester. The elastomer is SK Chemicals' G240D, a polyester-based elastomer rubber with a shore hardness of 40D, the plate-shaped kaolin is BASF's TR445 as an inorganic reinforcement, and the heat-resistant stabilizer is bis[4-(2-phenyl-2-propyl)phenyl]amine ( Bis[4-(2-phenyl-2-propyl)phenyl]amine) is Chemtura's Nauguard 445, and antioxidant phenol-based antioxidant is tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy). Hydrocinnamate)]methane (tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane) is ADEKA's AO-60, and phosphorus-based antioxidant is tris(2,4-di-tert- Butylphenyl)pentaerythritol-di-phosphite (Tris(2,4-di-t-butylphenyl)-phosphite) is SONGNOX 1680 from Seongwon, and the lubricant is ethylene bis stearamide (EBS) from Shinwon Chemical. HI-Lube and carbon black use Woosung Chemical's SEB2050 as the carbon black master batch.

composition Comparative Example 1
(weight%) Comparative Example 2
(weight%) Comparative Example 3
(weight%) Comparative Example 4
(weight%) Comparative Example 5
(weight%) Comparative Example 6
(weight%) Example 1
(weight%) Example 2
(weight%) profit polypropylene - 10 40 27 20 20 20 30 ECO 100 - - - - - - rubber MA-g EPDM - 70 40 60 60 60 60 50 polyester elastomer - 10 10 10 10 10 10 10 mineral plate-shaped kaolin - 7 7 - 7 12 7 7 heat stabilizer - 2 2 2 2 2 2 2 Antioxidants (phenol-based/phosphorus-based) - 0.2/0.2 0.2/0.2 0.2/0.2 0.2/0.2 0.2/0.2 0.2/0.2 0.2/0.2 active - 0.2 0.2 0.2 0.2 0.2 0.2 0.2 carbon black - One One One One One One One

To evaluate the physical properties of the thermoplastic resin compositions for air intake hoses of Comparative Examples 1 to 6 and Example 1 prepared above, specific gravity, tensile strength, elongation, flexural strength, flexural modulus, impact strength, Shore hardness properties were evaluated and the results were presented.

Specifically, to evaluate the physical properties of the thermoplastic resin composition for an air intake hose of the present invention, dumbbell-shaped specimen No. 3 was prepared according to the KS standard, and each physical property was measured according to the corresponding ASTM standard shown in Table 2 below.

'NB', shown as the impact strength value in Table 2 below, is an abbreviation for 'No Break' and indicates that the specimen is not broken.

item Experiment method
(ASTM) unit
(Unit) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example
2 importance D792 - 1.45 0.95 0.94 0.98 0.91 1.00 0.96 0.97 tensile strength D638 kgf/ ^cm2 100 60 50 170 90 200 130 150 elongation D638 % 200 600 >600 300 500 150 450 400 Flexural strength D790 kgf/ ^cm2 - 20 10 100 40 130 60 80 Flexural modulus of elasticity D790 kgf/ ^cm2 - 800 600 6000 1800 7000 3000 4500 Impact strength (23℃) D648 J/m N.B. N.B. N.B. N.B. N.B. 150 N.B. N.B. Showa hardness Share A - 70 80 72 90 75 95 85 88

According to the results in Table 2, Examples 1 and 2 of the present invention, like Comparative Example 1, have higher mechanical rigidity and flexural modulus characteristics compared to the case of the conventional ECO composition consisting only of epichlorohydrin rubber. And it showed excellent hardness, and the specific gravity was low, so it was confirmed that the weight reduction effect was improved.

In the case where the content of polypropylene, which is an impact block copolymer, was 10% by weight as a resin raw material as in Comparative Example 2, and in the case where plate-shaped kaolin was not added as an inorganic reinforcement as in Comparative Examples 1 and 4, Examples 1 and 2 It was confirmed that the flexural strength and flexural modulus were lower compared to .

As in Comparative Example 3, when ethylene propylene rubber (EPDM) grafted with maleic anhydride was 40% by weight as a rubber raw material, and when 12% by weight of plate-shaped kaolin was added as an inorganic reinforcement as in Comparative Example 6, Examples 1 and 2 When compared to the bar, which shows a low elongation value, problems with molding processability may occur, and in particular, as a result of the impact strength test, the specimens were not broken in the remaining Comparative Examples 1 to 5 and Examples 1 and 2, but Comparative Example 6 In the case of , the impact strength was 150 J/m, so it was confirmed that the mechanical rigidity was poor.

As seen, the thermoplastic resin composition for an air intake hose according to an embodiment of the present invention not only has high durability and excellent heat resistance compared to the comparative example, but is also lightweight.

It can be seen that the mechanical rigidity, flexural modulus characteristics, and excellent hardness have been improved, and physical properties such as weight reduction have been improved.

Figure 2 is an exemplary diagram of an air intake hose according to an embodiment of the present invention.

As shown in Figure 2, the air cleaner connection part 230 of the air intake hose to which the thermoplastic resin composition for air intake of the present invention is applied is directly connected to the engine connection part 210 by high-temperature heat fusion. Therefore, since there is no need for a separate connection structure such as the bellows 120 as in the conventional air intake hose, the parts can be further lightweighted along with the weight reduction of the material.

The specific techniques discussed above are only preferred implementation examples and are not limited to the above-described examples and attached drawings. Therefore, various substitutions and changes are possible without departing from the technical spirit of the present invention.

110: Conventional engine connection
120: Conventional bellows
130: Conventional air cleaner connection part
210: Engine connection part
230: Air cleaner connection part

Claims (7)

20 to 30% by weight of polypropylene-based impact block copolymer;
50 to 60% by weight of ethylene propylene rubber grafted with maleic anhydride;
10 to 20% by weight of polyester-based elastomer having a shore hardness of 40D;
5 to 10% by weight of plate-shaped kaolin as an inorganic reinforcing material;
1 to 3% by weight of Bis[4-(2-phenyl-2-propyl)phenyl]amine as a heat-resistant stabilizer;
0.3 to 0.5% by weight of at least one antioxidant selected from phenolic antioxidants and phosphorus antioxidants;
0.2 to 0.5% by weight of olefin-based lubricant; and
Contains 1 to 2% by weight of carbon black,
The phenolic antioxidant is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)(1,3,5-Trimethyl-2 ,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), 1,6-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propion Amido]hexane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane) and 1,6-bis[3-(3,5-di-tert- At least one selected from butyl-4-hydroxyphenyl)propionamido]propane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane),
The phosphorus-based antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite (Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di- phosphite) and bis(2,4-di-tert-butylphenyl)pentaerythritol-di-phosphite. A thermoplastic resin composition for an air intake hose characterized by: delete delete delete delete delete delete

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