KR101267830B1 - Elastomer composition - Google Patents

Elastomer composition Download PDF

Info

Publication number
KR101267830B1
KR101267830B1 KR1020120133680A KR20120133680A KR101267830B1 KR 101267830 B1 KR101267830 B1 KR 101267830B1 KR 1020120133680 A KR1020120133680 A KR 1020120133680A KR 20120133680 A KR20120133680 A KR 20120133680A KR 101267830 B1 KR101267830 B1 KR 101267830B1
Authority
KR
South Korea
Prior art keywords
rubber
weight
parts
fluorine
oxide
Prior art date
Application number
KR1020120133680A
Other languages
Korean (ko)
Inventor
박정배
이범철
최현경
Original Assignee
국방과학연구소
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 국방과학연구소 filed Critical 국방과학연구소
Priority to KR1020120133680A priority Critical patent/KR101267830B1/en
Application granted granted Critical
Publication of KR101267830B1 publication Critical patent/KR101267830B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/68—Plasticizers; Solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

Abstract

PURPOSE: A rubber composition is provided to be able to be used at a high temperature of 400 deg. C or more, and to minimize the degradation of mechanical property due to the improved heat resistance by selecting basic rubber materials and compounding agents. CONSTITUTION: A rubber composition comprises: fluorine rubber; an acid scavenger consisting of calcium hydroxide(Ca(OH)2); at least one cross-linking support agent selected from the group consisting of magnesium oxide(MgO), calcium oxide(CaO), and lead oxide(PbO); at least one flame retardant selected from the group consisting of antimony oxide(Sb2O3), aluminum hydroxide(Al(OH)3), and magnesium hydroxide(Mg(OH)2). The flame retardant is included at the amount of 5-10 parts by weight to 100.0 parts by weight of fluorine rubber. The fluorine content of the fluorine rubber is 65-71%.

Description

고무 조성물{ELASTOMER COMPOSITION}Rubber composition {ELASTOMER COMPOSITION}

본 발명은 내열성이 향상된 고온용 고무 조성물에 관한 것이다.The present invention relates to a high temperature rubber composition with improved heat resistance.

탄성중합체인 고무는 일반적으로 낮은 온도에서는 장기간 사용이 가능하나, 온도가 높아짐에 따라 고무의 사용 가능 시간은 줄어들게 되며 어느 정도 이상의 온도가 되면 폴리머의 분해에 의해 고무로써의 성능을 잃어버리게 된다.In general, rubber, which is an elastomer, can be used for a long time at a low temperature, but as the temperature increases, the usable time of the rubber decreases, and when the temperature becomes a certain temperature, the rubber performance is lost by decomposition of the polymer.

고무의 최대 사용 가능 온도는 고무의 원료인 폴리머의 종류에 따라 정해지게 되며, 내열성이 우수한 것으로 알려져 있는 과불소고무의 사용온도는 250℃까지인 것으로 알려져 있다.The maximum usable temperature of the rubber is determined according to the type of polymer which is a rubber raw material, and the use temperature of perfluorinated rubber, which is known to be excellent in heat resistance, is known to be up to 250 ° C.

따라서 고무의 사용 가능 온도를 높이기 위해서 대부분의 고무들은 고무 원료에 별도의 첨가제를 혼합하여 제조되나, 현재까지 알려진 고온 환경에서의 고무의 사용 가능 온도는 약 300℃ 내외로써 그보다 고온인 약 400℃ 이상에서 사용 가능한 조건은 만족하지 못하고 있다.Therefore, in order to increase the usable temperature of the rubber, most rubbers are manufactured by mixing a separate additive with the rubber raw material, but the usable temperature of the rubber in the high temperature environment known to the present is about 300 ° C or higher and about 400 ° C or higher. The conditions available in are not satisfied.

본 발명의 일 목적은 내열성이 크게 향상된 고온용 고무 조성물을 제공하기 위한 것이다.One object of the present invention is to provide a high temperature rubber composition with significantly improved heat resistance.

본 발명의 다른 일 목적은 내열성 향상에 따른 고무 조성물의 기계적 물성 하락을 최소화하기 위한 것이다.Another object of the present invention is to minimize the deterioration of mechanical properties of the rubber composition according to the improved heat resistance.

이와 같은 본 발명의 일 목적을 달성하기 위하여, 본 발명의 일 실시예에 따르는 고무 조성물은 불소고무, 제산제, 산화마그네슘(MgO), 산화칼슘(CaO), 산화납(PbO)으로 이루어진 군으로부터 선택된 적어도 하나의 가교보조제, 및 산화안티몬(Sb2O3), 수산화알루미늄(Al(OH)3), 수산화마그네슘(Mg(OH)2)으로 이루어진 군으로부터 선택된 적어도 하나의 난연제를 포함한다.In order to achieve one object of the present invention, the rubber composition according to an embodiment of the present invention is selected from the group consisting of fluorine rubber, antacid, magnesium oxide (MgO), calcium oxide (CaO), lead oxide (PbO). At least one crosslinking aid and at least one flame retardant selected from the group consisting of antimony oxide (Sb 2 O 3 ), aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ).

본 발명과 관련한 일 예에 따르면, 상기 불소고무는 불소 함량이 65~71%이다.According to an example related to the present invention, the fluorine rubber has a fluorine content of 65 to 71%.

본 발명과 관련한 다른 일 예에 따르면, 상기 제산제는 상기 불소고무 100중량부에 대하여 수산화칼슘(Ca(OH)2) 15~20중량부이다.According to another example related to the present invention, the antacid is 15 to 20 parts by weight of calcium hydroxide (Ca (OH) 2 ) based on 100 parts by weight of the fluorine rubber.

본 발명과 관련한 다른 일 예에 따르면, 상기 가교보조제는 상기 불소고무 100중량부에 대하여 5~10중량부이다.According to another example related to the present invention, the crosslinking aid is 5 to 10 parts by weight based on 100 parts by weight of the fluorine rubber.

본 발명과 관련한 다른 일 예에 따르면, 상기 난연제는 상기 불소고무 100중량부에 대하여 5~10중량부이다.According to another example related to the present invention, the flame retardant is 5 to 10 parts by weight based on 100 parts by weight of the fluororubber.

본 발명과 관련한 다른 일 예에 따르면, 상기 불소고무 100중량부에 대하여 충전제인 카본블랙 10~15중량부를 더 포함할 수 있다.According to another example related to the present invention, the filler may further include 10 to 15 parts by weight of carbon black, which is a filler, based on 100 parts by weight of the fluororubber.

상기와 같은 구성의 본 발명에 의하면, 고무 조성물은 400℃ 이상의 온도에서도 고무로써의 성능을 잃지 않으므로 400℃ 이상의 고온에서도 사용 가능하다.According to the present invention having the above-described configuration, the rubber composition can be used even at a high temperature of 400 ° C or higher since the rubber composition does not lose its performance even at a temperature of 400 ° C or higher.

또한 본 발명은, 기본 고무 재료의 선정 및 배합제의 선택을 통해 내열성 향상에 따른 기계적 물성의 하락을 최소화할 수 있다.In addition, the present invention, through the selection of the base rubber material and the selection of the compounding agent can minimize the decrease in mechanical properties due to the improved heat resistance.

도 1은 본 발명의 실시예2에 따른 고무 시편의 내열 시험 후 상태를 나타내는 형상 사진.
도 2는 본 발명의 실시예8에 따른 고무 시편의 내열 시험 후 상태를 나타내는 형상 사진.1 is a shape photograph showing a state after a heat test of a rubber specimen according to Example 2 of the present invention.
Figure 2 is a shape photograph showing a state after the heat test of the rubber specimens according to Example 8 of the present invention.

이하, 본 발명에 관련된 고무 조성물에 대하여 보다 상세하게 설명한다. 본 명세서에서 사용되는 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.EMBODIMENT OF THE INVENTION Hereinafter, the rubber composition which concerns on this invention is demonstrated in detail. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

본 발명의 일 실시예에 따르는 고무 조성물은 불소고무, 제산제, 가교보조제 및 난연제를 포함한다.The rubber composition according to an embodiment of the present invention includes a fluororubber, an antacid, a crosslinking aid and a flame retardant.

불소고무는 고무원료로써 불소함량이 65~71%이다. 일반적으로 불소고무의 성형 가류에는 비스페놀 가류(Bisphenol Curing), 과산화물 가류(Peroxide Curing), 트리아진 가류(Triazine Curing) 세 가지 가류 방법이 적용된다. 그러나 이들 세 가지 가류 방법의 가장 큰 단점은 300℃ 이상의 고온상태에서 폴리머와 폴리머 사이의 결합구조가 쉽게 깨져 고무로써의 성능을 잃어버린다는 점이다. 따라서 불소고무는 본 발명에서 목표로 하는 400℃ 이상의 고온에서도 고무로써의 성능을 유지하는 고무 조성물을 도출하기 위해 불소고무의 원료에 자체적으로 가류제가 포함되어 있는 것을 사용하는 것이 바람직하다.Fluorine rubber is a rubber raw material and has a fluorine content of 65 to 71%. In general, three vulcanization methods are applied to the molded vulcanized vulcanized rubber, such as bisphenol cure, peroxide cure, and triazine cure. However, the major disadvantage of these three vulcanization methods is that the bonding structure between the polymer and the polymer is easily broken at high temperatures of 300 ° C. or higher, thereby losing its performance as a rubber. Therefore, in order to derive a rubber composition which maintains the performance as a rubber even at a high temperature of 400 ° C. or higher, which is the object of the present invention, it is preferable to use a vulcanizing rubber having a vulcanizing agent in itself.

제산제는 고무 조성물의 가류 과정에서 불소에 의해 발생할 수 있는 고무의 열적특성 변화를 감소시키기 위한 것으로, 본 발명에서의 제산제는 수산화칼슘(Ca(OH)2)을 사용한다. 수산화칼슘은 불소고무 100중량부에 대하여 15~20중량부를 사용하는 것이 바람직하다.Antacids are intended to reduce changes in the thermal properties of rubber that may be caused by fluorine in the vulcanization process of the rubber composition. The antacids in the present invention use calcium hydroxide (Ca (OH) 2 ). It is preferable to use 15-20 weight part of calcium hydroxide with respect to 100 weight part of fluororubbers.

가교보조제(가황촉진제)는 고무 조성물의 가류시 불소고무에 포함되어 있는 가류제와 병용되어 가류를 촉진시킨다. 가교보조제는 고무의 기계적 물성치를 보완하고 내열특성을 향상시킨다. 본 발명에서의 가교보조제는 산화마그네슘(MgO), 산화칼슘(CaO), 산화납(PbO)을 단독으로 사용하거나 서로 혼합하여 사용할 수 있다. 가교보조제는 지나치게 많이 첨가할 경우 고무의 기계적 물성을 저하시킬 수 있으므로 불소고무 100중량부에 대하여 5~10중량부를 사용하는 것이 바람직하다.The crosslinking aid (vulcanization accelerator) is used together with the vulcanizing agent contained in the fluorine rubber during vulcanization of the rubber composition to promote vulcanization. Crosslinking aids complement the mechanical properties of rubber and improve its heat resistance. The crosslinking aid in the present invention may be used alone or mixed with magnesium oxide (MgO), calcium oxide (CaO), lead oxide (PbO). It is preferable to use 5 to 10 parts by weight with respect to 100 parts by weight of fluororubber because the crosslinking aid may lower the mechanical properties of the rubber when added too much.

난연제는 고무의 열적 특성을 증가시키기 위한 것으로써 크게 반응형 난연제와 첨가형 난연제 두 가지 종류가 있다. 반응형 난연제는 고무 또는 플라스틱과 화학적으로 반응시켜 상기 고무 또는 플라스틱과 일체화되는 것이고, 첨가형 난연제는 고무 또는 플라스틱과 물리적으로 혼합시켜 난연성을 얻는 것이다. 본 발명에서는 첨가형 난연제를 적용하는 방법으로 무기물 난연제인 산화 안티몬(Sb2O3) 또는 수산화화합물 종류인 수산화알루미늄(Al(OH)3), 수산화마그네슘(Mg(OH)2)을 단독으로 사용하거나 서로 혼합하여 사용할 수 있다. 난연제는 불소고무 100중량부에 대하여 5~10중량부를 사용하는 것이 바람직하다.Flame retardants are intended to increase the thermal properties of rubber. There are two types of flame retardants and additive flame retardants. Reactive flame retardants are chemically reacted with rubber or plastic to integrate with the rubber or plastic, and additive flame retardants are physically mixed with rubber or plastic to obtain flame retardancy. In the present invention, an inorganic flame retardant, antimony oxide (Sb 2 O 3 ) or a hydroxide compound, aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ) may be used alone or as a method of applying an additive flame retardant. Can be mixed with each other. It is preferable to use 5-10 weight part with respect to 100 weight part of fluororubbers for a flame retardant.

고무 조성물은 기계적 물성 또는 성형가공성을 개선시키기 위해 충전제를 더 포함할 수 있다. 충전제는, 예를 들어 카본블랙 중 MT등급(중립열분해, Medium Thermal)일 수 있으며, 불소고무 100중량부에 대하여 10~15중량부를 사용할 수 있다.The rubber composition may further include a filler to improve mechanical properties or molding processability. The filler may be, for example, MT grade (medium thermal decomposition) in carbon black, and 10 to 15 parts by weight may be used based on 100 parts by weight of fluororubber.

고무 조성물은 첨가제를 더 포함할 수 있다. 첨가제는, 예를 들어 고무에 광택성을 부가하기 위하여 카르바나왁스(C-Wax)를 불소고무 100중량부에 대하여 1~5중량부를 사용할 수 있다.The rubber composition may further comprise an additive. The additive may be, for example, 1 to 5 parts by weight of carbana wax (C-Wax) based on 100 parts by weight of fluororubber in order to add glossiness to the rubber.

이하, 내열성이 향상된 고온용 고무 조성물에 대한 구체적인 내용을 실시예를 통해 확인하도록 한다.Hereinafter, specific details of the high temperature rubber composition having improved heat resistance will be confirmed through the examples.

하기의 표 1 및 표 2에서 고무원료를 선택하고, 표 3 내지 표 6에서 고무 원료에 첨가되는 배합제를 선택한다.In Table 1 and Table 2 below, the rubber raw material is selected, and in Tables 3 to 6, the compounding agent added to the rubber raw material is selected.

표 1은 고무원료를 서로 달리 선택한 비교예를 나타낸 표이고, 표 2는 표 1에 기재된 비교예의 기계적 및 열적 물성 측정값을 나타낸 표이다.Table 1 is a table showing a comparative example of differently selected rubber raw materials, Table 2 is a table showing the measured mechanical and thermal properties of the comparative example described in Table 1.

(단위:중량부) 구분(Unit: weight part) 비교예1Comparative Example 1 비교예2Comparative Example 2
고무
Rubber
NBR고무(ACN 41%)NBR rubber (ACN 41%) -- 100100 불소고무(불소함향 65%)Fluorine rubber (65% fluorine content) 100100 -- 불소고무(불소함량 50%)Fluorine rubber (Fluorine content 50%) -- -- 충전제Filler 카본불랙(MT-C)Carbon Black (MT-C) 1212 1212
가교보조제
Crosslinking aid
산화마그네슘(MgO)Magnesium Oxide (MgO) 33 1010 산화칼슘(CaO)Calcium Oxide (CaO) -- -- 산화납(PbO)Lead oxide (PbO) -- -- 제산제Antacid 수산화칼슘(Ca(OH)2)Calcium hydroxide (Ca (OH) 2 ) 66 1515
난연제
Flame retardant
산화안티몬(Sb2O3)Antimony Oxide (Sb 2 O 3 ) -- -- 수산화알루미늄(Al(OH)3)Aluminum hydroxide (Al (OH) 3 ) -- -- 수산화마그네슘(Mg(OH)2)Magnesium Hydroxide (Mg (OH) 2 ) -- -- 합계Sum 121121 137137

비교예1은 불소함량이 65%인 불소고무를 고무원료로 사용하고, 불소고무 100중량부에 대하여 충전제로써 MT 등급의 카본블랙(MT-C) 12중량부, 가교보조제로써 산화마그네슘 3중량부, 제산제로써 수산화칼슘 6중량부를 사용하였다.In Comparative Example 1, fluorine rubber containing 65% of fluorine was used as a rubber raw material, 12 parts by weight of MT black carbon (MT-C) as a filler, and 3 parts by weight of magnesium oxide as a crosslinking aid based on 100 parts by weight of fluorine rubber. 6 parts by weight of calcium hydroxide was used as an antacid.

비교예2는 아크릴로니트릴(ACN) 함량이 41%인 니트릴부타디엔고무(NBR고무)를 고무원료로 사용하고, 니트릴부타디엔고무 100중량부에 대하여 충전제로써 MT 등급의 카본블랙 12중량부, 가교보조제로써 산화마그네슘 10중량부, 제산제로써 수산화칼슘 15중량부를 사용하였다.In Comparative Example 2, nitrile butadiene rubber (NBR rubber) having 41% acrylonitrile (ACN) content was used as a rubber raw material, and 12 parts by weight of MT black carbon black as a filler was used as a filler based on 100 parts by weight of nitrile butadiene rubber and a crosslinking aid. 10 parts by weight of magnesium oxide was used, and 15 parts by weight of calcium hydroxide was used as an antacid.

비교예1 및 비교예2는 고무원료를 선택하기 위한 것으로 난연제는 첨가하지 않았다.Comparative Example 1 and Comparative Example 2 are for selecting a rubber raw material, and no flame retardant was added.

하기의 표 2는 표 1에 기재된 비교예1 및 비교예2의 물성을 측정한 결과이다. 표 2를 포함한 하기의 표 4 및 표 6에서의 내열/내유성 시험 후 물성 값은 공통적으로 항공유(합성) 연료를 사용하여 온도 400℃에서 10분동안 가열 한 후 측정한 값이다. 마찬가지로 경도는 쇼어 경도계(Shore A type)로 측정한 값이다.Table 2 below shows the results of measuring physical properties of Comparative Example 1 and Comparative Example 2 described in Table 1. After the heat / oil resistance test in Tables 4 and 6, including Table 2, the physical properties are measured after heating at 400 ° C. for 10 minutes using air fuel (synthetic) fuel. Similarly, hardness is measured with a Shore A type.

항목Item 단위unit 비교예1Comparative Example 1 비교예2Comparative Example 2
기본물성
Basic property
경도Hardness PointPoint 7676 3535 인장강도The tensile strength kgf/㎠kgf / cm2 124124 2525 신장율Elongation rate %% 233233 5050 내열/내유성
시험 후
물성Heat / Oil Resistance
After the test
Properties 경도Hardness PointPoint
300℃
이상의 온도에서
용융되어
물성측정불가
300 ° C
At temperatures above
Melted
Property measurement not possible
300℃
도달 전에
용융되어
물성측정불가
300 ° C
Before reaching
Melted
Property measurement not possible 인장강도The tensile strength kgf/㎠kgf / cm2 신장율Elongation rate %%
변화
change
경도변화Hardness change PointPoint 인장강도변화율Tensile Strength Change Rate %% 신장율변화율Elongation rate %%

표 2의 비교예1과 비교예2를 비교하면 불소함량이 65%인 불소고무를 고무원료로 사용한 비교예1은 300℃까지는 사용이 가능하나, 300℃ 이후로 고무의 표면이 용융되기 기작하여 400℃에서는 고무의 형태를 유지하지 못한 채 녹아내리게 된다. 아크릴로니트릴 함량이 41%인 니트릴부타디엔고무를 사용한 비교예2는 300℃에 도달하기 전에 용융되므로, 본 발명에서 내열성을 고무의 내열성을 향상시키기 위해서는 불소고무를 사용하는 것이 바람직한 것을 알 수 있다.Comparing Comparative Example 1 and Comparative Example 2 in Table 2, Comparative Example 1 using fluorine rubber having a fluorine content of 65% as a rubber raw material can be used up to 300 ° C., but the surface of the rubber melts after 300 ° C. At 400 ° C, the rubber melts without maintaining its shape. Since Comparative Example 2 using nitrile butadiene rubber having an acrylonitrile content of 41% is melted before reaching 300 ° C., it can be seen that it is preferable to use fluorine rubber in order to improve the heat resistance of rubber in the present invention.

하기의 표 3은 난연제를 첨가하지 않고 충전제, 가교보조제 및 제산제의 배합비의 변경에 따른 실시예를 나타낸 것이다.Table 3 below shows an example of changing the blending ratio of the filler, crosslinking aid and antacid without adding a flame retardant.

(단위:중량부) 구분(Unit: weight part) 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6
고무
Rubber
NBR고무(ACN 41%)NBR rubber (ACN 41%) -- -- -- -- -- -- 불소고무(불소함향 65%)Fluorine rubber (65% fluorine content) 100100 100100 100100 100100 100100 -- 불소고무(불소함량 50%)Fluorine rubber (Fluorine content 50%) -- -- -- -- -- 100100 충전제Filler 카본불랙(MT-C)Carbon Black (MT-C) 1212 1212 1212 1212 1212 1212
가교보조제
Crosslinking aid
산화마그네슘(MgO)Magnesium Oxide (MgO) 55 1010 1515 -- 55 -- 산화칼슘(CaO)Calcium Oxide (CaO) -- -- -- 88 -- -- 산화납(PbO)Lead oxide (PbO) -- -- -- -- 44 1010 제산제Antacid 수산화칼슘(Ca(OH)2)Calcium hydroxide (Ca (OH) 2 ) 1515 1515 1515 2020 2020 2525
난연제
Flame retardant
산화안티몬(Sb2O3)Antimony Oxide (Sb 2 O 3 ) -- -- -- -- -- -- 수산화알루미늄(Al(OH)3)Aluminum hydroxide (Al (OH) 3 ) -- -- -- -- -- -- 수산화마그네슘(Mg(OH)2)Magnesium Hydroxide (Mg (OH) 2 ) -- -- -- -- -- -- 합계Sum 132132 137137 142142 140140 141141 147147

실시예1 내지 실시예6은 공통적으로 불소고무를 사용하였으나, 실시예1 내지 실시예5는 불소의 함량이 65%이고, 실시예6은 불소의 함량이 50%이다. 실시예1 내지 실시예6은 공통적으로 불소고무 100중량부에 대하여 충전제로써 카본블랙(MT-C) 12중량부를 사용하였다.Although Examples 1 to 6 commonly used fluorine rubber, Examples 1 to 5 had a fluorine content of 65% and Example 6 had a fluorine content of 50%. Examples 1 to 6 commonly used 12 parts by weight of carbon black (MT-C) as a filler based on 100 parts by weight of fluororubber.

실시예1은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 5중량부를 사용하고 제산제로써 수산화칼슘 15중량부를 사용하였다.In Example 1, 5 parts by weight of magnesium oxide was used as a crosslinking aid and 100 parts by weight of calcium hydroxide was used as an antacid based on 100 parts by weight of fluorine rubber.

실시예2는 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 10중량부를 사용하고 제산제로써 수산화칼슘 15중량부를 사용하였다.In Example 2, 10 parts by weight of magnesium oxide was used as a crosslinking aid and 100 parts by weight of calcium hydroxide was used as an antacid based on 100 parts by weight of fluorine rubber.

실시예3은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 15중량부를 사용하고 제산제로써 수산화칼슘 15중량부를 사용하였다.In Example 3, 15 parts by weight of magnesium oxide was used as a crosslinking aid and 15 parts by weight of calcium hydroxide was used as an antacid based on 100 parts by weight of fluorine rubber.

실시예4는 불소고무 100중량부에 대하여, 가교보조제로써 산화칼슘 8중량부를 사용하고 제산제로써 수산화칼슘 20중량부를 사용하였다.In Example 4, 8 parts by weight of calcium oxide was used as a crosslinking aid, and 20 parts by weight of calcium hydroxide was used as an antacid, based on 100 parts by weight of fluorine rubber.

실시예5는 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘과 산화납을 각각 5중량부와 4중량부로 혼합하여 사용하고 제산제로써 수산화칼슘 20중량부를 사용하였다.In Example 5, magnesium oxide and lead oxide were mixed at 5 parts by weight and 4 parts by weight, respectively, as a crosslinking aid, and 100 parts by weight of calcium hydroxide was used as 100 parts by weight of fluorine rubber.

실시예6은 불소고무 100중량부에 대하여, 가교보조제로써 산화납 10중량부를 사용하고 제산제로써 수산화칼슘 25중량부를 사용하였다.In Example 6, 10 parts by weight of lead oxide was used as a crosslinking aid and 100 parts by weight of calcium hydroxide was used as an antacid based on 100 parts by weight of fluororubber.

도 1은 본 발명의 실시예2에 따른 고무 시편의 내열 시험 후상태를 나타낸 형상사진이고, 표 4는 표 3에 기재된 실시예의 기계적 및 열적 물성 측정값을 나타낸 것이다.1 is a shape photograph showing the state after the heat test of the rubber specimens according to Example 2 of the present invention, Table 4 shows the mechanical and thermal properties measurements of the examples described in Table 3.

항목Item 단위unit 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6
기본물성
Basic property
경도Hardness PointPoint 7575 7676 7575 7676 7575 7676 인장강도The tensile strength kgf/㎠kgf / cm2 122122 127127 124124 124124 124124 124124 신장율Elongation rate %% 212212 196196 208208 233233 208208 233233 내열/내유
시험 후
물성Heat / oil resistant
After the test
Properties 경도Hardness PointPoint
물성
측정
불가
Properties
Measure
Impossible


물성
측정
불가
Properties
Measure
Impossible


물성
측정
불가
Properties
Measure
Impossible


물성
측정
불가
Properties
Measure
Impossible


물성
측정
불가
Properties
Measure
Impossible


물성
측정
불가
Properties
Measure
Impossible

인장강도The tensile strength kgf/㎠kgf / cm2 신장율Elongation rate %%
변화
change
경도변화Hardness change PointPoint 인장강도 변화율Tensile Strength Change Rate %% 신장율 변화율Elongation rate of change %%

도 1을 참조하면 가교보조제의 첨가량이 증가함에 따라, 400℃에서도 고무 고유의 형상을 유지하는 것을 확인할 수 있다. 이는 가교보조제의 첨가량이 고무 조성물의 내열특성의 향상에 영향을 미치는 것을 의미한다. 그러나 표 4에 나타난 바와 같이 실시예1 내지 실시예6은 400℃에서 10분간 가열한 후에는 용융되어 물성을 측정할 수 없다.Referring to Figure 1 it can be seen that as the addition amount of the crosslinking assistant increases, maintaining the shape of the rubber inherent even at 400 ℃. This means that the addition amount of the crosslinking aid affects the improvement of the heat resistance property of the rubber composition. However, as shown in Table 4, Examples 1 to 6 are melted after heating at 400 ° C. for 10 minutes, and thus physical properties cannot be measured.

하기의 표 5은 충전제, 가교보조제, 제산제 및 난연제의 배합비의 변경에 따른 실시예를 나타낸 것이다.Table 5 below shows an example according to the change in the mixing ratio of the filler, crosslinking aid, antacid and flame retardant.

(단위:중량부) 구분(Unit: weight part) 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10 실시예11Example 11
고무
Rubber
NBR고무(ACN 41%)NBR rubber (ACN 41%) -- -- -- -- -- 불소고무(불소함향 65%)Fluorine rubber (65% fluorine content) 100100 100100 100100 100100 100100 불소고무(불소함량 50%)Fluorine rubber (Fluorine content 50%) -- -- -- -- -- 충전제Filler 카본불랙(MT-C)Carbon Black (MT-C) 1212 1212 1212 1212 1212
가교보조제
Crosslinking aid
산화마그네슘(MgO)Magnesium Oxide (MgO) 66 66 66 33 33 산화칼슘(CaO)Calcium Oxide (CaO) 33 산화납(PbO)Lead oxide (PbO) 33 제산제Antacid 수산화칼슘(Ca(OH)2)Calcium hydroxide (Ca (OH) 2 ) 1818 1818 1818 1818 1818
난연제
Flame retardant
산화안티몬(Sb2O3)Antimony Oxide (Sb 2 O 3 ) 55 1010 1515 수산화알루미늄(Al(OH)3)Aluminum hydroxide (Al (OH) 3 ) 88 44 수산화마그네슘(Mg(OH)2)Magnesium Hydroxide (Mg (OH) 2 ) 44 합계Sum 141141 146146 151151 144144 144144

실시예7 내지 실시예11은 공통적으로 불소함량 65%의 불소고무를 고무원료로 사용하고, 충전제로써 카본블랙을 불소고무 100중량부에 대하여 12중량부 첨가하였다. 그리고 제산제로써 수산화칼슘을 불소고무 100중량부에 대하여 18중량부 첨가하였다.Examples 7 to 11 commonly used fluorine rubber having a fluorine content of 65% as a rubber raw material, and 12 parts by weight of carbon black was added to 100 parts by weight of fluorine rubber as a filler. And 18 weight part of calcium hydroxide was added with respect to 100 weight part of fluororubbers as an antacid.

실시예7은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 6중량부를 사용하고 난연제로써 산화안티몬 5중량부를 사용하였다.In Example 7, 6 parts by weight of magnesium oxide was used as a crosslinking assistant and 5 parts by weight of antimony oxide as a flame retardant based on 100 parts by weight of fluorine rubber.

실시예8은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 6중량부를 사용하고 난연제로써 산화안티몬 10중량부를 사용하였다.In Example 8, 6 parts by weight of magnesium oxide was used as a crosslinking aid and 100 parts by weight of antimony oxide as a flame retardant based on 100 parts by weight of fluorine rubber.

실시예9는 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘 6중량부를 사용하고 난연제로써 산화안티몬 15중량부를 사용하였다.In Example 9, 6 parts by weight of magnesium oxide was used as a crosslinking aid and 100 parts by weight of antimony oxide was used as a flame retardant based on 100 parts by weight of fluorine rubber.

실시예10은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘과 산화칼슘을 3중량부씩 혼합하여 사용하고 난연제로써 수산화알루미늄 8중량부를 사용하였다.In Example 10, 3 parts by weight of magnesium oxide and calcium oxide were mixed as a crosslinking aid with respect to 100 parts by weight of fluorine rubber, and 8 parts by weight of aluminum hydroxide was used as a flame retardant.

실시예11은 불소고무 100중량부에 대하여, 가교보조제로써 산화마그네슘과 산화납을 3중량부씩 혼합하여 사용하였고 난연제로써 수산화알루미늄과 수산화마그네슘을 4중량부씩 혼합하여 사용하였다.In Example 11, magnesium oxide and lead oxide were mixed by 3 parts by weight with respect to 100 parts by weight of fluorine rubber, and 4 parts by weight of aluminum hydroxide and magnesium hydroxide were used as a flame retardant.

도 2는 본 발명의 실시예8에 따른 고무 시편의 내열 시험 후 상태를 나타내는 형상 사진이고, 하기의 표 4는 표 3에 기재된 실시예의 기계적 및 열적 물성 측정값을 나타낸 것이다.Figure 2 is a shape photograph showing the state after the heat test of the rubber specimens according to Example 8 of the present invention, Table 4 below shows the mechanical and thermal properties measured values of the examples described in Table 3.

항목Item 단위unit 실시예7Example 7 실시예8Example 8 실시예9Example 9 실시예10Example 10 실시예11Example 11
기본물성
Basic property
경도Hardness PointPoint 7878 7777 7878 7777 7575 인장강도The tensile strength kgf/㎠kgf / cm2 142142 133133 138138 136136 126126 신장율Elongation rate %% 250250 216216 232232 230230 198198 내열/내유
시험 후
물성Heat / oil resistant
After the test
Properties 경도Hardness PointPoint 5858 5656 5555 5858 5757 인장강도The tensile strength kgf/㎠kgf / cm2 102102 108108 9090 106106 104104 신장율Elongation rate %% 130130 105105 112112 9898 108108
변화
change
경도변화Hardness change PointPoint -20-20 -21-21 -23-23 -19-19 -18-18 인장강도 변화율Tensile Strength Change Rate %% -28-28 -19-19 -35-35 -22-22 -17-17 신장율 변화율Elongation rate of change %% -8-8 -21-21 -19-19 -28-28 -14-14

도 2를 참조하면 불소고무에 충전제, 가교보조제, 제산제, 난연제를 투입하여 가류한 결과 400℃의 온도에서 내열시험을 거친 후에도 고무 고유의 형상을 유지하고 있음을 알 수 있다.Referring to FIG. 2, the filler, crosslinking aid, antacid, and flame retardant were added to the fluorine rubber to be vulcanized. As a result, the shape of the rubber was maintained even after the heat test at 400 ° C.

이는 표 6에도 나타나 있는 것과 같이 400℃에서 10분간 내열 시험을 거친 후에도 물성 측정이 가능한 것으로부터 알 수 있는 것과 마찬가지이다.This is similar to what can be seen from the physical property measurement after the heat test at 400 ° C. for 10 minutes as shown in Table 6.

표 6을 참조하면, 실시예7 내지 실시예11은 인장강도가 내열 시험 전 대비 15~35%, 신장율은 내열 시험 전 대비 10~30% 내외에서 변화를 나타낸다. 이것은 배합제에 따라 내열 특성 향상에 따른 기계적 물성의 감소를 나타낸다.Referring to Table 6, Examples 7 to 11 show a change in tensile strength of about 15 to 35%, and an elongation rate of about 10 to 30% compared to before the heat test. This indicates a decrease in mechanical properties with improved heat resistance depending on the formulation.

표 6의 실시예7 내지 실시예11에서 나타난 바와 같이 불소고무 100중량부에 대하여 가교보조제 5~10중량부, 제산제 15~20중량부, 난연제 5~10중량부가 혼합된 고무 조성물은 400℃ 이상의 고온에서 고무의 성능을 잃어버리지 않으므로 내열성이 크게 향상된다. 또한 실시예11과 같이 난연제를 단독으로 사용하는 경우보다 2종 이상을 혼합하여 사용한 경우 기계적 물성 하락치가 상대적으로 적어 다른 실시예에 비하여 우수한 결과를 나타낸다.As shown in Examples 7 to 11 of Table 6, a rubber composition containing 5 to 10 parts by weight of a crosslinking aid, 15 to 20 parts by weight of an antacid, and 5 to 10 parts by weight of a flame retardant based on 100 parts by weight of fluorine rubber is 400 ° C or higher. Heat resistance is greatly improved since the rubber performance is not lost at high temperatures. In addition, when using two or more kinds of mixed flame retardant alone as in Example 11, the mechanical properties of the lower value is relatively less than the other examples show excellent results.

이상에서 설명된 고무 조성물은 상기 설명된 실시예들의 구성과 방법에 한정되는 것이 아니라, 상기 실시예들은 다양한 변형이 이루어질 수 있도록 각 실시예들의 전부 또는 일부가 선택적으로 조합되어 구성될 수도 있다.The rubber composition described above is not limited to the configuration and method of the above-described embodiments, but the embodiments may be configured by selectively combining all or part of the embodiments so that various modifications can be made.

Claims (6)

불소고무;
수산화칼슘(Ca(OH)2)으로 이루어진 제산제;
산화마그네슘(MgO), 산화칼슘(CaO), 산화납(PbO)으로 이루어진 군으로부터 선택된 적어도 하나의 가교보조제; 및
산화안티몬(Sb2O3), 수산화알루미늄(Al(OH)3), 수산화마그네슘(Mg(OH)2)으로 이루어진 군으로부터 선택된 적어도 하나의 난연제를 포함하고,
상기 난연제는 상기 불소고무 100중량부에 대하여 5~10중량부를 포함하는 것을 특징으로 하는 고무 조성물.Fluorine rubber;
Antacid consisting of calcium hydroxide (Ca (OH) 2 );
At least one crosslinking aid selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and lead oxide (PbO); And
At least one flame retardant selected from the group consisting of antimony oxide (Sb 2 O 3 ), aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ),
The flame retardant is a rubber composition, characterized in that it comprises 5 to 10 parts by weight based on 100 parts by weight of the fluororubber. 제1항에 있어서,
상기 불소고무는 불소 함량이 65~71%인 것을 특징으로 하는 고무 조성물.The method of claim 1,
The fluorine rubber is a rubber composition, characterized in that the fluorine content is 65 ~ 71%. 제1항에 있어서,
상기 제산제는 상기 불소고무 100중량부에 대하여 수산화칼슘(Ca(OH)2) 15~20중량부인 것을 특징으로 하는 고무 조성물.The method of claim 1,
The antacid is a rubber composition, characterized in that 15 to 20 parts by weight of calcium hydroxide (Ca (OH) 2 ) with respect to 100 parts by weight of the fluorine rubber. 제1항에 있어서,
상기 가교보조제는 상기 불소고무 100중량부에 대하여 5~10중량부를 포함하는 것을 특징으로 하는 고무 조성물.The method of claim 1,
The crosslinking assistant is a rubber composition, characterized in that it comprises 5 to 10 parts by weight based on 100 parts by weight of the fluororubber. 삭제delete 제1항에 있어서,
상기 불소고무 100중량부에 대하여 충전제인 카본블랙 10~15중량부를 더 포함하는 것을 특징으로 하는 고무 조성물.The method of claim 1,
10 to 15 parts by weight of carbon black, which is a filler, based on 100 parts by weight of the fluororubber.
KR1020120133680A 2012-11-23 2012-11-23 Elastomer composition KR101267830B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020120133680A KR101267830B1 (en) 2012-11-23 2012-11-23 Elastomer composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020120133680A KR101267830B1 (en) 2012-11-23 2012-11-23 Elastomer composition

Publications (1)

Publication Number Publication Date
KR101267830B1 true KR101267830B1 (en) 2013-05-27

Family

ID=48666916

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020120133680A KR101267830B1 (en) 2012-11-23 2012-11-23 Elastomer composition

Country Status (1)

Country Link
KR (1) KR101267830B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115572485A (en) * 2022-08-02 2023-01-06 西北工业大学 Anti-radiation fluorosilicone rubber composite material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001342318A (en) * 2000-06-01 2001-12-14 Matsushita Electric Ind Co Ltd Fluororubber composition, fixing member, fixing method, and fixing apparatus
JP2006524740A (en) * 2003-04-25 2006-11-02 ミリケン・アンド・カンパニー Antibacterial unvulcanized rubber composition and antibacterial vulcanized rubber article

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001342318A (en) * 2000-06-01 2001-12-14 Matsushita Electric Ind Co Ltd Fluororubber composition, fixing member, fixing method, and fixing apparatus
JP2006524740A (en) * 2003-04-25 2006-11-02 ミリケン・アンド・カンパニー Antibacterial unvulcanized rubber composition and antibacterial vulcanized rubber article

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115572485A (en) * 2022-08-02 2023-01-06 西北工业大学 Anti-radiation fluorosilicone rubber composite material and preparation method thereof

Similar Documents

Publication Publication Date Title
EP2033990B1 (en) Nitrile rubber composition, crosslinkable nitrile rubber composition and crosslinked rubber
CN106470836A (en) Laminate
KR101662007B1 (en) An abrasion resistive rubber composition for shoes outsole and method for thereof
CN103275439A (en) Ageing-resistant HPVC foaming sole material
JP6121995B2 (en) Method for producing heat-stabilized polyamide-filled acrylate polymer
JP2007291295A (en) Water proofing nitrile rubber composition
KR101267830B1 (en) Elastomer composition
KR101914143B1 (en) Rubber composition for cellular phone testing holder having flame retardant and electrically conductivity
US5447992A (en) Heat and ozone resistant NBR/epichlorohydrin blends
AU2016294055B2 (en) Rubber composition for flame-retardant hose, and flame-retardant hose
TW201807041A (en) Rubber composition for hose and hose
KR101829449B1 (en) Composition for fluororubber having excellent mechanical strength
JP2006226389A (en) Packing for acrylic rubber connector
KR101230058B1 (en) Manufacturing method of diffuser membrane for improved elasticity and durability and high efficiency diffuser membrane using thereof
TWI437040B (en) Improved polymer vulcanizate and process for the production thereof
KR20140145749A (en) Rubber composition for outsole
JPH09111047A (en) Heat-resistant butadiene/acrylonitrile-polyvinyl chloride blend
KR20120130634A (en) A Rubber Composition for Engine Mount
KR100314755B1 (en) Excellent Thermal Conductive Rubber Compound for Bladder
KR20160046359A (en) Bladder rubber composition for vulcanizing tire
KR101267942B1 (en) Rubber components of O-ring for refrigerant compressor
JP2007002010A (en) Polymer composition and molded material consisting of the same
KR101458046B1 (en) The electrically insulated mat and method for producing the same
KR102119543B1 (en) Hose used cooling system having high temperature resistant and high durability
KR101653758B1 (en) Composite of rubber for o-ring and manufacturing method of the same

Legal Events

Date Code Title Description
A201 Request for examination
A302 Request for accelerated examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20190502

Year of fee payment: 7