WO2024090626A1 - Radiator hose composition for vehicle - Google Patents

Radiator hose composition for vehicle Download PDF

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Publication number
WO2024090626A1
WO2024090626A1 PCT/KR2022/016707 KR2022016707W WO2024090626A1 WO 2024090626 A1 WO2024090626 A1 WO 2024090626A1 KR 2022016707 W KR2022016707 W KR 2022016707W WO 2024090626 A1 WO2024090626 A1 WO 2024090626A1
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Prior art keywords
weight
parts
rubber
epdm
radiator hose
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PCT/KR2022/016707
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French (fr)
Korean (ko)
Inventor
최혜경
권오희
김철홍
김강민
송진선
성권욱
김효준
박건욱
유재근
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(주)한국팬트라
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Publication of WO2024090626A1 publication Critical patent/WO2024090626A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K11/00—Arrangement in connection with cooling of propulsion units
    • B60K11/02—Arrangement in connection with cooling of propulsion units with liquid cooling
    • B60K11/04—Arrangement or mounting of radiators, radiator shutters, or radiator blinds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/322—Liquid component is processing oil

Definitions

  • the present invention relates to a radiator hose composition for automobiles.
  • the radiator hose is a hose used as a transfer path for coolant that connects the engine and the radiator to cool the engine and engine oil. It is composed of a composite of inner rubber, braided yarn, and outer rubber, and has high temperature durability, liquid resistance, and pressure resistance. etc. are required.
  • EPDM-based composite rubber materials To improve heat resistance in EPDM-based composite rubber materials, there are common methods such as applying EPDM with high molecular weight and low ENB content, increasing the content of paraffin-based processing oil, and applying a peroxide cross-linking system.
  • organic polymers are added to gelled clay through hydration and cation exchange of water-swellable clay in molten EPDM. It is manufactured by adding and mixing nanoclay and carbon black obtained by adding a topical agent to exfoliate to form nanoparticles and then drying them, the water-swellable clay is bentonite, and the organicizing agent is Na 2 CO 3 or Na 2 SiO 3 is starting.
  • the present invention was invented to solve the above-mentioned problems, and the technical problem is to provide a radiator hose composition for automobiles that improves high-temperature durability to cope with high-efficiency engines.
  • the present invention is a composition of 3 to 10 parts by weight of a compatibilizer, based on 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber.
  • a radiator hose composition for an automobile characterized in that it comprises 100 to 120 parts by weight of carbon black, 10 to 50 parts by weight of calcium carbonate, and 30 to 50 parts by weight of a hydrocarbon-based process oil with a paraffin structure content of 70% or more.
  • the calcium carbonate has a particle size of 0.1 ⁇ m or less and is surface-treated with fatty acid.
  • the compatibilizer is characterized in that it is modified EPDM (modified EPDM).
  • the interface between EPDM rubber and silicone rubber is controlled to enhance compatibility to form a rubber composition that can secure high temperature durability above 150 °C, and this is applied to an automobile radiator hose. There is an effect that can be utilized.
  • the present invention relates to a radiator hose composition for automobiles.
  • the radiator hose composition of the present invention contains 3 to 10 parts by weight of a compatibilizer and 100 to 100 parts by weight of carbon black, based on 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber. It is characterized in that it is formed by comprising 120 parts by weight, 10 to 50 parts by weight of calcium carbonate with a particle size of 0.1 ⁇ m or less and surface treated with fatty acid, and 30 to 50 parts by weight of hydrocarbon-based process oil with a paraffin structure content of 70% or more.
  • the rubber base forms the base of the radiator hose composition and consists of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber.
  • EPDM ethylene propylene diene monomer
  • the amount of EPDM rubber is less than 80 parts by weight or more than 95 parts by weight, there is a disadvantage in that an excessive amount of compatibilizer must be used due to a decrease in miscibility with silicone rubber. Not only does the internal pressure of the radiator hose decrease, but the radiator hose may crack when observing high temperature durability. This can happen.
  • the amount of silicone rubber is less than 5 parts by weight or exceeds 20 parts by weight, the physical properties of the radiator hose composition may be impaired due to low miscibility with EPDM rubber.
  • the amount of silicone rubber exceeds 20 parts by weight, there is a problem of increased unit price, so 20 parts by weight It is desirable to add not to exceed the amount.
  • the high-part substrate is formed by mixing 80 to 95 parts by weight and 5 to 20 parts by weight of EPDM rubber and silicone rubber, respectively.
  • Modified EPDM is a product in which functional compounds such as maleic anhydride and acrylic acid are grafted onto the ends of EPDM, and is similar to EPDM rubber. It functions as a compatibilizer that allows polymers of different polarities to mix well.
  • modified EPDM is a compatibilizer and can be contained in the range of 3 to 10 parts by weight based on 100 parts by weight of the rubber base. If modified EPDM is mixed in an amount of less than 3 parts by weight based on 100 parts by weight of the rubber base, the miscibility between EPDM rubber and silicone rubber cannot be increased and the productability as a radiator hose is not achieved. If it exceeds 10 parts by weight, the radiator hose composition is not suitable for use. It is necessary to be careful about adding excessive amounts as it can deteriorate high temperature durability characteristics.
  • Carbon black can improve the reinforcement properties of radiator hose compositions and have a beneficial effect on physical properties such as hardness, tensile strength, and elongation. If the carbon black is outside the range of 100 to 120 parts by weight based on 100 parts by weight of the rubber base, the hardness, tensile strength, and elongation values required for the radiator hose cannot be satisfied.
  • Calcium carbonate has a particle size of 0.1 ⁇ m or less and is surface-treated with fatty acid, and may be included in the range of 10 to 50 parts by weight based on 100 parts by weight of the rubber base.
  • the radiator hose composition will have poor moldability due to lower extrudability, and if it exceeds 50 parts by weight, it may greatly affect the physical properties of the radiator hose and is not desirable. not.
  • paraffin-based process oils with excellent heat resistance and a paraffin structure content of 63 to 69% and an aromatic structure content of 2 to 5% are used.
  • paraffin-based process oils with excellent heat resistance are used.
  • Hydrocarbon-based process oil with a paraffin structure content of 70% or more can be mixed in the range of 30 to 50 parts by weight based on 100 parts by weight of the rubber base. If the paraffin structure content of the process oil is less than 70%, it is not effective in improving the heat resistance of the radiator hose. Also, even if less than 30 parts by weight of process oil is mixed, it is ineffective in increasing the heat resistance of the radiator hose. On the other hand, if the hydrocarbon-based process oil with a paraffin structure content of 70% or more exceeds 50 parts by weight based on 100 parts by weight of the rubber base, durability may be reduced when molded into a radiator hose.
  • a rubber base consisting of 95 parts by weight of EPDM rubber and 5 parts by weight of silicone rubber, 3 parts by weight of modified EPDM, 100 parts by weight of carbon black, 30 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ⁇ m or less and surface treated with fatty acid, 40 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes.
  • the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. .
  • the sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
  • a rubber base consisting of 85 parts by weight of EPDM rubber and 15 parts by weight of silicone rubber, 5 parts by weight of modified EPDM, 100 parts by weight of carbon black, 30 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ⁇ m or less and surface treated with fatty acid, 40 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes.
  • the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. .
  • the sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
  • a rubber base consisting of 95 parts by weight of EPDM rubber and 5 parts by weight of silicone rubber, 3 parts by weight of modified EPDM, 100 parts by weight of carbon black, 50 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ⁇ m or less and surface treated with fatty acid, 50 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes.
  • the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. .
  • the sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
  • a compound was prepared by mixing 2 parts by weight of polyethylene glycol and 1.5 parts by weight of an anti-aging agent at 100° C. for about 10 minutes using a kneader, a compound kneader.
  • the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. .
  • the sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
  • the rubber base consisting of 80 parts by weight of EPDM rubber and 20 parts by weight of silicone rubber, 100 parts by weight of carbon black, 30 parts by weight of light calcium carbonate with a particle size of 2 ⁇ m, paraffin structure content of 63%, and aromatic structure content of 5%.
  • 40 parts by weight of in-process oil, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were kneaded at 100°C for about 10 minutes using a compound kneader. Manufactured.
  • the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. .
  • the sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
  • Examples 1 to 3 produced specimens composed of radiator hose compositions by varying the components of the rubber base, Comparative Example 1 used only EPDM rubber as the rubber base, and Comparative Example 2 used EPDM rubber as the rubber base. 80 parts by weight and 20 parts by weight of silicone rubber were used, and Comparative Examples 1 and 2 had the same contents of zinc oxide, stearic acid, polyethylene glycol, anti-aging agent, peroxide cross-linking agent, and co-cross-linking agent as those of Examples 1 to 3, but modified EPDM was used.
  • a specimen consisting of a radiator hose composition was prepared by varying the ingredients, such as not adding any, and the specific formulation is summarized in Table 1 below. However, the unit is parts by weight.
  • Process oil 1) Process oil with a paraffin structure content of 63% and an aromatic structure content of 5% (Michang Petrochemical, P-3)
  • Process oil 2) Process oil with a paraffin structure content of 70% and an aromatic structure content of
  • Example 1 In this test example, the basic physical properties and accelerated aging tests of Examples 1 to 3 and Comparative Examples 1 and 3 were analyzed. In relation to this, the accelerated aging test was performed by subjecting the manufactured specimens to accelerated aging for 168 hours at a temperature of 150 ⁇ 1°C and then measuring the changes in characteristic values before and after accelerated aging. The results are shown in Table 2 below. .
  • Example Comparative example One 2 3 One 2 Properties Hardness (Hs) 67 67 68 68 67 tensile strength (MPa) 11.6 10.9 11.3 10.5 8.9 elongation rate (%) 360 330 350 320 270 Promotion Aging test Hardness change (Hs) +8 +5 +7 +13 +7 Tensile strength change rate (%) -29.8 -24.6 -26.7 -43.5 -30.7 Rate of change in elongation (%) -30.2 -28.9 -31.0 -50.8 -37.5
  • Examples 1 to 3 are overall superior to Comparative Examples 1 and 2, and Comparative Example 1 showed the lowest value in the accelerated aging test.
  • silicone rubber was applied and the accelerated aging test results were improved compared to Comparative Example 1, but the basic physical properties were low because EPDM rubber and silicone rubber did not mix well.
  • the present invention was developed using EPDM (ethylene rubber).
  • EPDM ethylene rubber
  • a rubber base consisting of 80 to 95 parts by weight of propylene diene monomer (rubber) and 5 to 20 parts by weight of silicone rubber
  • 3 to 10 parts by weight of modified EPDM 100 to 120 parts by weight of carbon black
  • the particle size is 0.1 ⁇ m or less. It is characterized by comprising 10 to 50 parts by weight of calcium carbonate surface-treated with fatty acid and 30 to 50 parts by weight of hydrocarbon-based process oil with a paraffin content of 70% or more.
  • the interface between EPDM rubber and silicone rubber is controlled to enhance compatibility, thereby forming a rubber composition that can secure high temperature durability above 150 °C, and it is expected that it can be used in automobile radiator hoses.

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  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to a radiator hose composition for a vehicle. The technical subject of the present invention is formed by comprising: with respect to 100 parts by weight of a rubber base consisting of 80-95 parts by weight of ethylene propylene diene monomer (EPDM) rubber and 5-20 parts by weight of silicone rubber, 3-10 parts by weight of a compatibilizer; 100-120 parts by weight of carbon black; 10-50 parts by weight of calcium carbonate having a particle size of 0.1 ㎛ or less and surface-treated with fatty acid; and 30-50 parts by weight of hydrocarbon-based process oil having a paraffin structure content of greater than or equal to 70%.

Description

자동차용 라디에이터 호스 조성물Automotive radiator hose composition
본 발명은 자동차용 라디에이터 호스 조성물에 관한 것이다.The present invention relates to a radiator hose composition for automobiles.
일반적으로 라디에이터 호스는 엔진과 라디에이터를 연결하여 엔진 및 엔진 오일을 냉각시켜주는 냉각수의 이송경로로 사용되는 호스로써, 내면고무, 편조사, 외면고무 등으로 복합체를 구성하고 고온내구성, 내액성 및 내압성 등이 요구된다.In general, the radiator hose is a hose used as a transfer path for coolant that connects the engine and the radiator to cool the engine and engine oil. It is composed of a composite of inner rubber, braided yarn, and outer rubber, and has high temperature durability, liquid resistance, and pressure resistance. etc. are required.
종래 라디에이터 호스의 소재로는 스타이렌부타다이엔 고무(SBR), 천연 고무(NR) 또는 클로로프렌 고무(CR) 등의 고무가 사용되었으나 자동차 엔진의 연비 향상을 위한 고성능화 및 고효율화에 따라, 열효율 개선을 위한 냉각수 관리 온도가 상승하게 되어 2000 년대 이후 에틸렌 프로필렌 디엔 모노머 고무(EPDM)로 교체되어 적용되고 있다.Conventionally, rubber such as styrene-butadiene rubber (SBR), natural rubber (NR), or chloroprene rubber (CR) was used as the material for radiator hoses, but with the increase in performance and efficiency to improve the fuel efficiency of automobile engines, thermal efficiency has been improved. As the temperature for cooling water management has increased, it has been replaced with ethylene propylene diene monomer rubber (EPDM) since the 2000s.
EPDM계 복합 고무소재에서 내열성을 향상시키기 위해, 분자량이 높고 ENB 함량이 낮은 EPDM을 적용하거나, 파라핀계 공정오일 함량을 높이고, 과산화물 가교시스템을 적용하는 등의 일반적인 방법이 있다.To improve heat resistance in EPDM-based composite rubber materials, there are common methods such as applying EPDM with high molecular weight and low ENB content, increasing the content of paraffin-based processing oil, and applying a peroxide cross-linking system.
예를 들면 '내열성과 내구성이 우수한 자동차 라디에이터호스고무 및 이를 위한 나노 콤포지트 조성물(KR 10-2009-0042631 A)'에서는 용융 상태의 EPDM에 수팽윤성 점토의 수화 및 양이온교환을 통해 겔화된 점토에 유기화제를 첨가하여 박리시켜 나노입자화한 후 건조하여 얻어진 나노클레이 및 카본블랙을 투입하고 혼합함으로써 제조되고, 상기 수팽윤성 점토가 벤토나이트이며, 상기 유기화제가 Na2CO3 또는 Na2SiO3인 기술을 개시하고 있다.For example, in 'Automotive radiator hose rubber with excellent heat resistance and durability and nanocomposite composition for the same (KR 10-2009-0042631 A)', organic polymers are added to gelled clay through hydration and cation exchange of water-swellable clay in molten EPDM. It is manufactured by adding and mixing nanoclay and carbon black obtained by adding a topical agent to exfoliate to form nanoparticles and then drying them, the water-swellable clay is bentonite, and the organicizing agent is Na 2 CO 3 or Na 2 SiO 3 is starting.
하지만 양이온교환 등의 겔화 과정을 거쳐야 하고, 상태물성, 압출성, 생산성 등의 문제로 인하여 내열성 향상에는 한계가 남아 있으므로, 이를 해결하기 위한 라디에이터 호스 조성물에 대한 기술 개발이 요구되고 있는 실정이다.However, there is a need to go through a gelation process such as cation exchange, and there are still limits to improving heat resistance due to problems with physical properties, extrudability, and productivity. Therefore, there is a need to develop technology for radiator hose compositions to solve this problem.
본 발명은 상기한 문제점을 해소하기 위하여 발명된 것으로, 고효율 엔진에 대응할 수 있도록 고온내구성이 향상될 수 있도록 하는 자동차용 라디에이터 호스 조성물을 제공하는 것을 기술적 해결과제로 한다.The present invention was invented to solve the above-mentioned problems, and the technical problem is to provide a radiator hose composition for automobiles that improves high-temperature durability to cope with high-efficiency engines.
상기의 기술적 과제를 해결하기 위하여 본 발명은, EPDM(ethylene propylene diene monomer) 고무 80 ~ 95 중량부와 실리콘 고무 5 ~ 20 중량부로 이루어진 고무 기재 100 중량부에 대하여, 상용화제 3 ~ 10 중량부, 카본블랙 100 ~ 120 중량부, 탄산칼슘 10 ~ 50 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 30 ~ 50 중량부를 포함하여 형성되는 것을 특징으로 하는, 자동차용 라디에이터 호스 조성물을 제공한다.In order to solve the above technical problem, the present invention is a composition of 3 to 10 parts by weight of a compatibilizer, based on 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber. Provided is a radiator hose composition for an automobile, characterized in that it comprises 100 to 120 parts by weight of carbon black, 10 to 50 parts by weight of calcium carbonate, and 30 to 50 parts by weight of a hydrocarbon-based process oil with a paraffin structure content of 70% or more.
본 발명에 있어서, 상기 탄산칼슘은, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 것을 특징으로 한다.In the present invention, the calcium carbonate has a particle size of 0.1 ㎛ or less and is surface-treated with fatty acid.
본 발명에 있어서, 상기 상용화제는, 개질된 EPDM((modified EPDM)인 것을 특징으로 한다.In the present invention, the compatibilizer is characterized in that it is modified EPDM (modified EPDM).
상기 과제의 해결 수단에 의한 본 발명에 따르면, EPDM 고무와 실리콘 고무 간의 계면이 제어되어 상용성을 강화시킴으로써 150 ℃ 이상에서 고온내구성을 확보할 수 있는 고무 조성물을 형성하고, 이를 자동차용 라디에이터 호스에 활용할 수 있는 효과가 있다.According to the present invention as a means of solving the above problem, the interface between EPDM rubber and silicone rubber is controlled to enhance compatibility to form a rubber composition that can secure high temperature durability above 150 ℃, and this is applied to an automobile radiator hose. There is an effect that can be utilized.
또한, 본 발명의 카본블랙, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 탄산칼슘 및 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일의 최적 조성을 통하여, 실리콘 고무 도입에 따른 배합 단가 상승을 방지하여 경제성을 확보할 수 있으며, 라디에이터 호스로의 압출성을 향상시킬 수 있는 효과가 있다.In addition, through the optimal composition of the carbon black of the present invention, a hydrocarbon-based process oil with a particle size of 0.1 ㎛ or less, calcium carbonate surface-treated with fatty acid, and a paraffin structure content of 70% or more, an increase in compounding cost due to the introduction of silicone rubber is prevented. It can secure economic feasibility and has the effect of improving extrusion into radiator hoses.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 실시예들을 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention can be subject to various changes and can have various forms, embodiments will be described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 갖는 것으로 해석되어야 하며, 본 명세서에서 명백하게 정의하지 않는 한 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as having an ideal or excessively formal meaning unless clearly defined in this specification. .
본 명세서에서 사용하는 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한 복수의 표현을 포함한다.The terms used herein are merely used to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.
본 발명은 자동차용 라디에이터 호스 조성물에 관한 것이다. 상기 본 발명의 라디에이터 호스 조성물은 EPDM(ethylene propylene diene monomer) 고무 80 ~ 95 중량부와 실리콘 고무 5 ~ 20 중량부로 이루어진 고무 기재 100 중량부에 대하여, 상용화제 3 ~ 10 중량부, 카본블랙 100 ~ 120 중량부, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 탄산칼슘 10 ~ 50 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 30 ~ 50 중량부를 포함하여 형성되는 것을 특징으로 한다.The present invention relates to a radiator hose composition for automobiles. The radiator hose composition of the present invention contains 3 to 10 parts by weight of a compatibilizer and 100 to 100 parts by weight of carbon black, based on 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber. It is characterized in that it is formed by comprising 120 parts by weight, 10 to 50 parts by weight of calcium carbonate with a particle size of 0.1 ㎛ or less and surface treated with fatty acid, and 30 to 50 parts by weight of hydrocarbon-based process oil with a paraffin structure content of 70% or more.
고무 기재는 라디에이터 호스 조성물의 베이스를 이루는 것으로, EPDM(ethylene propylene diene monomer) 고무 80 ~ 95 중량부와 실리콘 고무 5 ~ 20 중량부로 이루어진다.The rubber base forms the base of the radiator hose composition and consists of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber.
EPDM 고무가 80 중량부 미만이거나 95 중량부를 초과하면 실리콘 고무와의 혼화력 저하로 인해 상용화제를 과량 사용해야 하는 단점이 있으며, 라디에이터 호스의 내부압성이 저하될 뿐만 아니라 고온내구성 관전에서 라디에이터 호스에 크랙이 발생할 수 있다. 실리콘 고무가 5 중량부 미만이거나 20 중량부를 초과하면 EPDM 고무와의 낮은 혼화력으로 라디에이터 호스 조성물의 물성을 저해할 수 있으며, 특히 실리콘 고무가 20 중량부를 초과하게 되면 단가 상승의 문제점이 있어 20 중량부를 초과하지 않도록 첨가하는 것이 바람직하다. 상기 이유로, 고부 기재는 EPDM 고무와 실리콘 고무 각각은 80 ~ 95 중량부와 5 ~ 20 중량부로 혼합되는 형성되는 것이 바람직하다.If the amount of EPDM rubber is less than 80 parts by weight or more than 95 parts by weight, there is a disadvantage in that an excessive amount of compatibilizer must be used due to a decrease in miscibility with silicone rubber. Not only does the internal pressure of the radiator hose decrease, but the radiator hose may crack when observing high temperature durability. This can happen. If the amount of silicone rubber is less than 5 parts by weight or exceeds 20 parts by weight, the physical properties of the radiator hose composition may be impaired due to low miscibility with EPDM rubber. In particular, if the amount of silicone rubber exceeds 20 parts by weight, there is a problem of increased unit price, so 20 parts by weight It is desirable to add not to exceed the amount. For the above reasons, it is preferable that the high-part substrate is formed by mixing 80 to 95 parts by weight and 5 to 20 parts by weight of EPDM rubber and silicone rubber, respectively.
일반적으로 극성이 다른 고분자는 잘 혼화되지 않는 성질을 가지고 있는데, 이의 개선을 위해 상용화제가 사용되고 있으며, modified EPDM은 EPDM의 말단에 maleic anhydride, acrylic acid 등의 기능성 화합물을 그라프트한 것으로, EPDM 고무와 극성이 다른 고분자를 잘 혼화되도록 하는 상용화제의 기능을 한다.In general, polymers of different polarity do not mix well, and compatibilizers are used to improve this. Modified EPDM is a product in which functional compounds such as maleic anhydride and acrylic acid are grafted onto the ends of EPDM, and is similar to EPDM rubber. It functions as a compatibilizer that allows polymers of different polarities to mix well.
즉 modified EPDM는 상용화제로써 고무 기재 100 중량부에 대하여 3 ~ 10 중량부의 범위로 함유될 수 있다. modified EPDM이 고무 기재 100 중량부에 대하여 3 중량부 미만으로 혼합되면 EPDM 고무와 실리콘 고무와의 혼화력을 높일 수 없어 라디에이터 호스로의 제품성이 도출되지 않으며, 10 중량부를 초과하면 라디에이터 호스 조성물의 고온내구성 특성을 변질시킬 수 있어 과량 첨가하는 것은 주의할 필요성이 있다.That is, modified EPDM is a compatibilizer and can be contained in the range of 3 to 10 parts by weight based on 100 parts by weight of the rubber base. If modified EPDM is mixed in an amount of less than 3 parts by weight based on 100 parts by weight of the rubber base, the miscibility between EPDM rubber and silicone rubber cannot be increased and the productability as a radiator hose is not achieved. If it exceeds 10 parts by weight, the radiator hose composition is not suitable for use. It is necessary to be careful about adding excessive amounts as it can deteriorate high temperature durability characteristics.
카본블랙은 라디에이터 호스 조성물에 보강성을 개선하여 경도, 인장강도 및 신장율 등의 물성에 유리한 영향을 줄 수 있다. 카본블랙이 고무 기재 100 중량부에 대하여 100 ~ 120 중량부 범위를 벗어나면 라디에이터 호스에서 요구되는 경도, 인장강도 및 신장율 수치 값을 만족시킬 수 없게 된다.Carbon black can improve the reinforcement properties of radiator hose compositions and have a beneficial effect on physical properties such as hardness, tensile strength, and elongation. If the carbon black is outside the range of 100 to 120 parts by weight based on 100 parts by weight of the rubber base, the hardness, tensile strength, and elongation values required for the radiator hose cannot be satisfied.
탄산칼슘은 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 것으로, 고무 기재 100 중량부에 대하여 10 ~ 50 중량부의 범위로 포함될 수 있다.Calcium carbonate has a particle size of 0.1 ㎛ or less and is surface-treated with fatty acid, and may be included in the range of 10 to 50 parts by weight based on 100 parts by weight of the rubber base.
일반적으로 1 ~ 3 ㎛의 입자크기를 갖는 경질 탄산칼슘이 많이 사용되고 있으나, 본 발명에서는 물성 영향을 최소화하고 압출성을 향상시키기 위하여 탄산칼슘의 입자 크기가 0.1 ㎛ 이하가 되도록 하였으며, 지방산으로 표면처리하여 표면개질이 이루어진 극미세 탄산칼슘을 사용한다.In general, light calcium carbonate with a particle size of 1 to 3 ㎛ is widely used, but in the present invention, in order to minimize the effect on physical properties and improve extrudability, the particle size of calcium carbonate was set to 0.1 ㎛ or less, and the surface was treated with fatty acid. Therefore, ultrafine calcium carbonate with surface modification is used.
탄산칼슘이 고무 기재 100 중량부에 대하여 10 중량부 미만으로 첨가되면 라디에이터 호스 조성물이 압출성 저하로 성형성이 좋지 못하게 되며, 50 중량부를 초과하면 라디에이터 호스의 물성에 많은 영향을 끼칠 수 있어 바람직하지 않다.If calcium carbonate is added in an amount of less than 10 parts by weight based on 100 parts by weight of the rubber base, the radiator hose composition will have poor moldability due to lower extrudability, and if it exceeds 50 parts by weight, it may greatly affect the physical properties of the radiator hose and is not desirable. not.
보통 파라핀, 나프텐, 아로마틱 구조를 가지는 탄화수소계 프로세스 오일 중 내열성이 우수한 파라핀 구조 함량이 63 ~ 69 %이고 아로마틱 구조 함량이 2 ~ 5 %인 파라핀계 프로세스 오일을 사용하고 있으나, 본 발명에서는 파라핀 구조 함량이 70 % 이상이고 아로마틱 구조 함량이 0 %인 탄화수소계 프로세스 오일을 사용한다.Usually, among hydrocarbon-based process oils with paraffin, naphthene, and aromatic structures, paraffin-based process oils with excellent heat resistance and a paraffin structure content of 63 to 69% and an aromatic structure content of 2 to 5% are used. However, in the present invention, paraffin-based process oils with excellent heat resistance are used. Use hydrocarbon-based process oil with a content of more than 70% and an aromatic structure content of 0%.
파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일은 고무 기재 100 중량부에 대해서 30 ~ 50 중량부 범위로 혼합될 수 있으며, 프로세스 오일의 파라핀 구조 함량이 70 % 미만이면 라디에이터 호스의 내열성 개선에 효과적이지 못하고 또한 프로세스 오일이 30 중량부 미만으로 혼합되어도 라디에이터 호스의 내열성을 높이는데 효과가 없다. 반면, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일이 고무 기재 100 중량부에 대해 50 중량부를 초과하면 라디에이터 호스로 성형 시 오히려 내구성 저하를 초래할 수 있다.Hydrocarbon-based process oil with a paraffin structure content of 70% or more can be mixed in the range of 30 to 50 parts by weight based on 100 parts by weight of the rubber base. If the paraffin structure content of the process oil is less than 70%, it is not effective in improving the heat resistance of the radiator hose. Also, even if less than 30 parts by weight of process oil is mixed, it is ineffective in increasing the heat resistance of the radiator hose. On the other hand, if the hydrocarbon-based process oil with a paraffin structure content of 70% or more exceeds 50 parts by weight based on 100 parts by weight of the rubber base, durability may be reduced when molded into a radiator hose.
상기와 같은 본 발명의 카본블랙, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 탄산칼슘 및 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일의 최적 조성을 통하여, 실리콘 고무 도입에 따른 배합 단가 상승을 방지하여 경제성을 확보할 수 있으며, 또한 라디에이터 호스로의 압출성을 향상시킬 수 있는 장점이 있다.Through the optimal composition of the carbon black of the present invention as described above, a hydrocarbon-based process oil with a particle size of 0.1 ㎛ or less, calcium carbonate surface-treated with fatty acid, and a paraffin structure content of more than 70%, an increase in compounding cost due to the introduction of silicone rubber is prevented. This ensures economic efficiency and also has the advantage of improving extrusion into the radiator hose.
이하, 본 발명의 실시예를 더욱 상세하게 설명하면 다음과 같다. 단, 이하의 실시예는 본 발명의 이해를 돕기 위하여 예시하는 것일 뿐, 이에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in more detail as follows. However, the following examples are merely illustrative to aid understanding of the present invention and are not intended to limit the scope of the present invention.
<실시예 1><Example 1>
EPDM 고무 95 중량부, 실리콘 고무 5 중량부로 이루어지는 고무 기재 100 중량부에 대하여 modified EPDM 3 중량부, 카본블랙 100 중량부, 입자크기 0.1 ㎛ 이하이고 지방산으로 표면처리된 극미세 탄산칼슘 30 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 40 중량부 및 산화아연 5 중량부, 스테아린산 2 중량부, 폴리에틸렌글리콜 2 중량부, 노화방지제 1.5 중량부를 컴파운드 혼련기인 니더(kneader)를 이용하여 100 ℃에서 약 10 분 동안 혼련하여 컴파운드를 제조하였다. 니더 작업이 끝난 컴파운드는 약 24 시간 상온에 방치하여 숙성시킨 후, 오픈 롤밀에서 과산화물 가교제 2 중량부, 공가교제 0.5 중량부를 추가 혼합하여 5 분 동안 균일하게 분산시킨 후 5 mm 시트상의 컴파운드를 제조하였다. 이렇게 제조된 시트상의 컴파운드를 시험규격에 따라 제작된 금형에 투입한 후 170 ℃, 150 kgf/cm2의 프레스 조건에서 약 10 분간 성형하여 시편을 제조하였다.For 100 parts by weight of a rubber base consisting of 95 parts by weight of EPDM rubber and 5 parts by weight of silicone rubber, 3 parts by weight of modified EPDM, 100 parts by weight of carbon black, 30 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ㎛ or less and surface treated with fatty acid, 40 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes. After the kneader work was completed, the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. . The sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
<실시예 2><Example 2>
EPDM 고무 85 중량부, 실리콘 고무 15 중량부로 이루어지는 고무 기재 100 중량부에 대하여 modified EPDM 5 중량부, 카본블랙 100 중량부, 입자크기 0.1 ㎛ 이하이고 지방산으로 표면처리된 극미세 탄산칼슘 30 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 40 중량부 및 산화아연 5 중량부, 스테아린산 2 중량부, 폴리에틸렌글리콜 2 중량부, 노화방지제 1.5 중량부를 컴파운드 혼련기인 니더(kneader)를 이용하여 100 ℃에서 약 10 분 동안 혼련하여 컴파운드를 제조하였다. 니더 작업이 끝난 컴파운드는 약 24 시간 상온에 방치하여 숙성시킨 후, 오픈 롤밀에서 과산화물 가교제 2 중량부, 공가교제 0.5 중량부를 추가 혼합하여 5 분 동안 균일하게 분산시킨 후 5 mm 시트상의 컴파운드를 제조하였다. 이렇게 제조된 시트상의 컴파운드를 시험규격에 따라 제작된 금형에 투입한 후 170 ℃, 150 kgf/cm2의 프레스 조건에서 약 10 분간 성형하여 시편을 제조하였다.For 100 parts by weight of a rubber base consisting of 85 parts by weight of EPDM rubber and 15 parts by weight of silicone rubber, 5 parts by weight of modified EPDM, 100 parts by weight of carbon black, 30 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ㎛ or less and surface treated with fatty acid, 40 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes. After the kneader work was completed, the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. . The sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
<실시예 3><Example 3>
EPDM 고무 95 중량부, 실리콘 고무 5 중량부로 이루어지는 고무 기재 100 중량부에 대하여 modified EPDM 3 중량부, 카본블랙 100 중량부, 입자크기 0.1 ㎛ 이하이고 지방산으로 표면처리된 극미세 탄산칼슘 50 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 50 중량부 및 산화아연 5 중량부, 스테아린산 2 중량부, 폴리에틸렌글리콜 2 중량부, 노화방지제 1.5 중량부를 컴파운드 혼련기인 니더(kneader)를 이용하여 100 ℃에서 약 10 분 동안 혼련하여 컴파운드를 제조하였다. 니더 작업이 끝난 컴파운드는 약 24 시간 상온에 방치하여 숙성시킨 후, 오픈 롤밀에서 과산화물 가교제 2 중량부, 공가교제 0.5 중량부를 추가 혼합하여 5 분 동안 균일하게 분산시킨 후 5 mm 시트상의 컴파운드를 제조하였다. 이렇게 제조된 시트상의 컴파운드를 시험규격에 따라 제작된 금형에 투입한 후 170 ℃, 150 kgf/cm2의 프레스 조건에서 약 10 분간 성형하여 시편을 제조하였다.For 100 parts by weight of a rubber base consisting of 95 parts by weight of EPDM rubber and 5 parts by weight of silicone rubber, 3 parts by weight of modified EPDM, 100 parts by weight of carbon black, 50 parts by weight of ultrafine calcium carbonate with a particle size of 0.1 ㎛ or less and surface treated with fatty acid, 50 parts by weight of hydrocarbon process oil with a paraffin structure content of 70% or more, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were mixed at 100°C using a kneader, a compound kneader. A compound was prepared by kneading for about 10 minutes. After the kneader work was completed, the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. . The sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
<비교예 1><Comparative Example 1>
EPDM 고무 100 중량부로 이루어지는 고무 기재 100 중량부에 대하여 카본블랙 120 중량부, 파라핀 구조 함량이 63 %이고 아로마틱 구조 함량이 5 %인 프로세스 오일 40 중량부 및 산화아연 5 중량부, 스테아린산 2 중량부, 폴리에틸렌글리콜 2 중량부, 노화방지제 1.5 중량부를 컴파운드 혼련기인 니더(kneader)를 이용하여 100 ℃에서 약 10 분 동안 혼련하여 컴파운드를 제조하였다. 니더 작업이 끝난 컴파운드는 약 24 시간 상온에 방치하여 숙성시킨 후, 오픈 롤밀에서 과산화물 가교제 2 중량부, 공가교제 0.5 중량부를 추가 혼합하여 5 분 동안 균일하게 분산시킨 후 5 mm 시트상의 컴파운드를 제조하였다. 이렇게 제조된 시트상의 컴파운드를 시험규격에 따라 제작된 금형에 투입한 후 170 ℃, 150 kgf/cm2의 프레스 조건에서 약 10 분간 성형하여 시편을 제조하였다.For 100 parts by weight of a rubber base consisting of 100 parts by weight of EPDM rubber, 120 parts by weight of carbon black, 40 parts by weight of process oil with a paraffin structure content of 63% and an aromatic structure content of 5%, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, A compound was prepared by mixing 2 parts by weight of polyethylene glycol and 1.5 parts by weight of an anti-aging agent at 100° C. for about 10 minutes using a kneader, a compound kneader. After the kneader work was completed, the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. . The sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
<비교예 2><Comparative Example 2>
EPDM 고무 80 중량부, 실리콘 고무 20 중량부로 이루어지는 고무 기재 100 중량부에 대하여 카본블랙 100 중량부, 입자크기 2 ㎛의 경질 탄산칼슘 30 중량부, 파라핀 구조 함량이 63 %이고 아로마틱 구조 함량이 5 %인 프로세스 오일 40 중량부 및 산화아연 5 중량부, 스테아린산 2 중량부, 폴리에틸렌글리콜 2 중량부, 노화방지제 1.5 중량부를 컴파운드 혼련기인 니더(kneader)를 이용하여 100 ℃에서 약 10 분 동안 혼련하여 컴파운드를 제조하였다. 니더 작업이 끝난 컴파운드는 약 24 시간 상온에 방치하여 숙성시킨 후, 오픈 롤밀에서 과산화물 가교제 2 중량부, 공가교제 0.5 중량부를 추가 혼합하여 5 분 동안 균일하게 분산시킨 후 5 mm 시트상의 컴파운드를 제조하였다. 이렇게 제조된 시트상의 컴파운드를 시험규격에 따라 제작된 금형에 투입한 후 170 ℃, 150 kgf/cm2의 프레스 조건에서 약 10 분간 성형하여 시편을 제조하였다.Based on 100 parts by weight of the rubber base consisting of 80 parts by weight of EPDM rubber and 20 parts by weight of silicone rubber, 100 parts by weight of carbon black, 30 parts by weight of light calcium carbonate with a particle size of 2 ㎛, paraffin structure content of 63%, and aromatic structure content of 5%. 40 parts by weight of in-process oil, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of polyethylene glycol, and 1.5 parts by weight of an anti-aging agent were kneaded at 100°C for about 10 minutes using a compound kneader. Manufactured. After the kneader work was completed, the compound was left at room temperature for about 24 hours to mature, and then 2 parts by weight of the peroxide cross-linker and 0.5 parts by weight of the co-cross-linker were additionally mixed in an open roll mill and dispersed uniformly for 5 minutes to prepare a 5 mm sheet-like compound. . The sheet-like compound prepared in this way was put into a mold manufactured according to the test standard, and then molded for about 10 minutes under press conditions of 170°C and 150 kgf/cm 2 to prepare a specimen.
상기한 바와 같이 실시예 1 ~ 3은 고무 기재의 성분을 달리 하여 라디에이터 호스 조성물로 이루어진 시편을 제조한 것이고, 비교예 1은 고무 기재로 EPDM 고무만을 사용하고, 비교예 2는 고무 기재로 EPDM 고무 80 중량부와 실리콘 고무 20 중량부를 사용한 것으로, 비교예 1 및 2는 실시예 1 ~ 3의 산화아연, 스테아린산, 폴리에틸렌글리콜, 노화방지제, 과산화물 가교제, 공가교제의 함량을 동일하게 하되, modified EPDM을 첨가하지 않는 등 성분들을 달리하여 라디에이터 호스 조성물로 이루어진 시편을 제조한 것으로, 구체적인 배합은 하기 표 1에 정리하여 나타내었다. 단, 단위는 중량부이다.As described above, Examples 1 to 3 produced specimens composed of radiator hose compositions by varying the components of the rubber base, Comparative Example 1 used only EPDM rubber as the rubber base, and Comparative Example 2 used EPDM rubber as the rubber base. 80 parts by weight and 20 parts by weight of silicone rubber were used, and Comparative Examples 1 and 2 had the same contents of zinc oxide, stearic acid, polyethylene glycol, anti-aging agent, peroxide cross-linking agent, and co-cross-linking agent as those of Examples 1 to 3, but modified EPDM was used. A specimen consisting of a radiator hose composition was prepared by varying the ingredients, such as not adding any, and the specific formulation is summarized in Table 1 below. However, the unit is parts by weight.
실시예Example 비교예Comparative example
1One 22 33 1One 22
EPDM 고무EPDM rubber 9595 8585 9595 100100 8080
실리콘 고무silicone rubber 55 1515 55 -- 2020
modified EPDMmodified EPDM 33 55 33 -- --
카본블랙carbon black 100100 100100 100100 120120 100100
탄산칼슘1) Calcium carbonate 1) -- -- -- -- 3030
탄산칼슘2) Calcium carbonate 2) 3030 3030 5050 -- --
프로세스 오일1) Process oil 1) -- -- -- 4040 4040
프로세스 오일2) Process oil 2) 4040 4040 5050 -- --
산화아연zinc oxide 55 55 55 55 55
스테아린산stearic acid 22 22 22 22 22
폴리에틸렌글리콜polyethylene glycol 22 22 22 22 22
노화방지제anti-aging agent 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5
과산화물 가교제peroxide crosslinking agent 22 22 22 22 22
공가교제public dating 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
탄산칼슘1): 입자크기 2 ㎛의 경질 탄산칼슘
탄산칼슘2): 입자크기 0.1 ㎛ 이하이고 지방산으로 표면처리된 극미세 탄산칼슘
프로세스 오일1): 파라핀 구조 함량이 63 %이고, 아로마틱 구조 함량이 5 %인 프로세스 오일(미창석유, P-3)
프로세스 오일2): 파라핀 구조 함량이 70 %이고, 아로마틱 구조 함량이 0 %인 프로세스 오일Calcium carbonate 1) : Light calcium carbonate with particle size of 2 ㎛
Calcium carbonate 2) : Ultrafine calcium carbonate with a particle size of 0.1 ㎛ or less and surface treated with fatty acid.
Process oil 1) : Process oil with a paraffin structure content of 63% and an aromatic structure content of 5% (Michang Petrochemical, P-3)
Process oil 2) : Process oil with a paraffin structure content of 70% and an aromatic structure content of 0%.
<시험예 1>본 시험예에서는 실시예 1 ~ 3과, 비교예 1 및 3의 기본 상태물성 및 촉진노화시험을 분석해 보았다. 관련해서 촉진노화시험은 제조된 시편을 150 ± 1 ℃의 온도에서 168 시간 동안 촉진노화를 실시한 후, 촉진노화 전/후의 특성값의 변화를 측정하여 나타내었으며, 그 결과를 하기 표 2에 나타내었다.<Test Example 1> In this test example, the basic physical properties and accelerated aging tests of Examples 1 to 3 and Comparative Examples 1 and 3 were analyzed. In relation to this, the accelerated aging test was performed by subjecting the manufactured specimens to accelerated aging for 168 hours at a temperature of 150 ± 1°C and then measuring the changes in characteristic values before and after accelerated aging. The results are shown in Table 2 below. .
실시예Example 비교예Comparative example
1One 22 33 1One 22
물성Properties 경도
(Hs)Hardness
(Hs) 		6767 6767 6868 6868 6767
인장강도
(MPa)tensile strength
(MPa) 		11.611.6 10.910.9 11.311.3 10.510.5 8.98.9
신장율
(%)elongation rate
(%) 		360360 330330 350350 320320 270270
촉진
노화
시험Promotion
Aging
test 		경도변화
(Hs)Hardness change
(Hs) 		+8+8 +5+5 +7+7 +13+13 +7+7
인장강도변화율
(%)Tensile strength change rate
(%) 		-29.8-29.8 -24.6-24.6 -26.7-26.7 -43.5-43.5 -30.7-30.7
신장율 변화율
(%)Rate of change in elongation
(%) 		-30.2-30.2 -28.9-28.9 -31.0-31.0 -50.8-50.8 -37.5-37.5
표 1의 기본 상태물성 및 촉진노화시험 결과에 따르면, 전반적으로 실시예 1 ~ 3이 비교예 1 및 2 보다 우수하며, 비교예 1의 경우 촉진노화시험에 따른 결과가 가장 낮은 수치를 나타내었고, 비교예 2의 경우 실리콘 고무가 적용되어 촉진노화시험 결과는 비교예 1에 비해 개선되었으나, EPDM 고무와 실리콘 고무가 잘 섞이지 않아 기본 상태물성이 낮은 결과를 나타냈다.정리하면, 본 발명은 EPDM(ethylene propylene diene monomer) 고무 80 ~ 95 중량부, 실리콘 고무 5 ~ 20 중량부로 이루어진 고무 기재 100 중량부에 대하여, modified EPDM 3 ~ 10 중량부, 카본블랙 100 ~ 120 중량부, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 탄산칼슘 10 ~ 50 중량부, 파라핀 함량이 70 % 이상인 탄화수소계 프로세스 오일 30 ~ 50 중량부를 포함하여 형성되는 특징이 있다.According to the basic physical properties and accelerated aging test results in Table 1, Examples 1 to 3 are overall superior to Comparative Examples 1 and 2, and Comparative Example 1 showed the lowest value in the accelerated aging test. In the case of Comparative Example 2, silicone rubber was applied and the accelerated aging test results were improved compared to Comparative Example 1, but the basic physical properties were low because EPDM rubber and silicone rubber did not mix well. In summary, the present invention was developed using EPDM (ethylene rubber). For 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of propylene diene monomer (rubber) and 5 to 20 parts by weight of silicone rubber, 3 to 10 parts by weight of modified EPDM, 100 to 120 parts by weight of carbon black, and the particle size is 0.1 ㎛ or less. It is characterized by comprising 10 to 50 parts by weight of calcium carbonate surface-treated with fatty acid and 30 to 50 parts by weight of hydrocarbon-based process oil with a paraffin content of 70% or more.
이러한 특징에 따르면, EPDM 고무와 실리콘 고무 간의 계면이 제어되어 상용성을 강화시킴으로써 150 ℃ 이상에서 고온내구성을 확보할 수 있는 고무 조성물을 형성하고, 이를 자동차용 라디에이터 호스에 활용할 수 있을 것으로 기대된다.According to these characteristics, the interface between EPDM rubber and silicone rubber is controlled to enhance compatibility, thereby forming a rubber composition that can secure high temperature durability above 150 ℃, and it is expected that it can be used in automobile radiator hoses.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서 본 발명에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라, 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것도 아니다. 본 발명의 보호 범위는 특허청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely an illustrative explanation of the technical idea of the present invention, and various modifications and variations will be possible to those skilled in the art without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but are for explanation, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection of the present invention should be interpreted in accordance with the scope of the patent claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims (3)

  1. EPDM(ethylene propylene diene monomer) 고무 80 ~ 95 중량부와 실리콘 고무 5 ~ 20 중량부로 이루어진 고무 기재 100 중량부에 대하여,With respect to 100 parts by weight of a rubber base consisting of 80 to 95 parts by weight of EPDM (ethylene propylene diene monomer) rubber and 5 to 20 parts by weight of silicone rubber,
    상용화제 3 ~ 10 중량부, 카본블랙 100 ~ 120 중량부, 탄산칼슘 10 ~ 50 중량부, 파라핀 구조 함량이 70 % 이상인 탄화수소계 프로세스 오일 30 ~ 50 중량부를 포함하여 형성되는 것을 특징으로 하는, 자동차용 라디에이터 호스 조성물.Characterized in that it is formed by comprising 3 to 10 parts by weight of a compatibilizer, 100 to 120 parts by weight of carbon black, 10 to 50 parts by weight of calcium carbonate, and 30 to 50 parts by weight of a hydrocarbon-based process oil with a paraffin structure content of 70% or more. Radiator hose composition for use.
  2. 제1 항에 있어서,According to claim 1,
    상기 탄산칼슘은, 입자크기가 0.1 ㎛ 이하이고 지방산으로 표면처리된 것을 특징으로 하는, 자동차용 라디에이터 호스 조성물.A radiator hose composition for automobiles, wherein the calcium carbonate has a particle size of 0.1 ㎛ or less and is surface-treated with fatty acid.
  3. 제1 항에 있어서,According to claim 1,
    상기 상용화제는, 개질된 EPDM((modified EPDM)인 것을 특징으로 하는, 자동차용 라디에이터 호스 조성물.The compatibilizer is a radiator hose composition for automobiles, characterized in that modified EPDM (modified EPDM).
PCT/KR2022/016707 2022-10-28 2022-10-28 Radiator hose composition for vehicle WO2024090626A1 (en)

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