KR102634410B1 - High heat resistance acrylic elastic material composition - Google Patents
High heat resistance acrylic elastic material composition Download PDFInfo
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- KR102634410B1 KR102634410B1 KR1020230124179A KR20230124179A KR102634410B1 KR 102634410 B1 KR102634410 B1 KR 102634410B1 KR 1020230124179 A KR1020230124179 A KR 1020230124179A KR 20230124179 A KR20230124179 A KR 20230124179A KR 102634410 B1 KR102634410 B1 KR 102634410B1
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- processing aid
- acrylic rubber
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000013013 elastic material Substances 0.000 title claims abstract description 27
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 48
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 48
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000004073 vulcanization Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims description 10
- -1 ether ester Chemical class 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 229940086560 pentaerythrityl tetrastearate Drugs 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 21
- 239000013527 degreasing agent Substances 0.000 abstract description 3
- 238000005237 degreasing agent Methods 0.000 abstract description 3
- 150000001804 chlorine Chemical group 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012795 verification Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000032912 Local swelling Diseases 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- JBQMAAJJRTWUPQ-UHFFFAOYSA-N 1,2-diphenylguanidine Chemical group C1(=CC=CC=C1)NC(NC1=CC=CC=C1)=N.C1(=CC=CC=C1)NC(=N)NC1=CC=CC=C1 JBQMAAJJRTWUPQ-UHFFFAOYSA-N 0.000 description 1
- ICYMHDUVBGVUPE-UHFFFAOYSA-N 1,2-diphenylguanidine;guanidine Chemical compound NC(N)=N.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 ICYMHDUVBGVUPE-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
본 발명은 고내열성 아크릴 탄성소재 조성물에 관한 것으로서, 더욱 상세하게는 CMB(Carbon Master Batch) 및 FMB(Final Master Batch)를 통해 제조되는 내열성 아크릴계 탄성소재 호스 조성물에 있어서, 상기 CMB에서는 아크릴 고무 100 중량부에 대하여 제1 카본필러 45 내지 55 중량부, 제2 카본필러 48 내지 55 중량부, 가소제 15 내지 10 중량부, 필러 1.5 내지 4.5 중량부, 제1 가공조제 4 내지 10 중량부 및 노방제 1.5 내지 2.5 중량부를 포함하고, 상기 FMB에서는 상기 아크릴 고무 100 중량부에 대하여 가류제 0.2 내지 0.3 중량부, 제2 가공조제 0.3 내지 0.5 중량부, 제3 가공조제 2.0 내지 2.6 중량부 및 가류지연제 0.1 내지 0.3 중량부를 포함하며, 상기 아크릴 고무는 염소 2% 함량의 활성화 염소계인 것을 특징으로 한다.
즉 본 발명은 활성화 염소계 아크릴 고무로 조성되는 호스 조성물을 개발함으로써 고내열성, 내한성 등의 물성을 향상시킬 수 있는 고내열성 아크릴 탄성소재 조성물을 제안하고자 한다.The present invention relates to a highly heat-resistant acrylic elastic material composition, and more specifically, to a heat-resistant acrylic elastic material hose composition manufactured through CMB (Carbon Master Batch) and FMB (Final Master Batch), wherein the CMB contains 100 weight of acrylic rubber. 45 to 55 parts by weight of the first carbon filler, 48 to 55 parts by weight of the second carbon filler, 15 to 10 parts by weight of the plasticizer, 1.5 to 4.5 parts by weight of the filler, 4 to 10 parts by weight of the first processing aid, and 1.5 parts by weight of the degreasing agent. to 2.5 parts by weight, and in the FMB, 0.2 to 0.3 parts by weight of a vulcanizing agent, 0.3 to 0.5 parts by weight of a second processing aid, 2.0 to 2.6 parts by weight of a third processing aid, and 0.1 part by weight of a vulcanization retardant, based on 100 parts by weight of the acrylic rubber. to 0.3 parts by weight, and the acrylic rubber is characterized in that it is an activated chlorine type with a chlorine content of 2%.
That is, the present invention seeks to propose a highly heat-resistant acrylic elastic material composition that can improve physical properties such as high heat resistance and cold resistance by developing a hose composition composed of activated chlorine-based acrylic rubber.
Description
본 발명은 아크릴 탄성소재(카르복실계) 고무로 조성되는 호스 조성물을 개발함으로써 고내열성, 내한성 등의 물성을 향상시킬 수 있는 고내열성 아크릴 탄성소재 조성물에 관한 것이다.The present invention relates to a highly heat-resistant acrylic elastic material composition that can improve physical properties such as high heat resistance and cold resistance by developing a hose composition composed of acrylic elastic material (carboxylic) rubber.
아크릴 고무 조성물은, 내열성ㆍ내유성이 우수하기 때문에 자동차의 엔진룸 내의 호스 부품이나 시일(seal) 부품에 사용되고 있다. 그러나 최근의 배기가스 대책, 엔진의 고출력화 등에 따라 사용 열적 조건이 더욱 엄격해졌기 때문에 지금까지 이상의 내열성이 요망되고 있다.Acrylic rubber compositions are used for hose parts and seal parts in the engine room of automobiles because they have excellent heat resistance and oil resistance. However, due to recent exhaust gas measures, higher engine output, etc., thermal conditions for use have become more stringent, and heat resistance beyond that achieved so far is required.
또한 미가황된 아크릴 고무는 혼련 시에 벤버리, 혼련기, 오픈 롤과 같은 혼련기의 금속면에 부착되기 쉽고, 혼련 후의 청소 처리가 필요한 경우가 종종 있다. 그 때문에 금속면으로의 점착이 적고, 가공성이 우수한 아크릴 고무가 요구되고 있다.Additionally, unvulcanized acrylic rubber tends to adhere to the metal surfaces of kneading machines such as banbury machines, kneaders, and open rolls during kneading, and cleaning treatment after kneading is often required. Therefore, acrylic rubber with low adhesion to metal surfaces and excellent processability is required.
가공성, 기계적 특성, 압축 영구 왜곡 특성, 내열성 등의 균형을 겸비한 아크릴 고무 재료로서, 카르복실기를 가교석(架橋席)으로 한 아크릴 고무 조성물이나, 아크릴 고무 조성물에 특정한 카본블랙을 배합하는 기술 등이 알려져 있다.As an acrylic rubber material with a balance of processability, mechanical properties, compression set properties, heat resistance, etc., acrylic rubber compositions with carboxyl groups as crosslinking stones and techniques for mixing specific carbon black into acrylic rubber compositions are known. there is.
또한 아크릴 고무의 내열성 개량에 대한 접근으로서, 아크릴 고무에 익스트림 엘라스토머(플루오로카본 고무, 플루오로 실리콘 고무, 실리콘 고무 등의 내열성이나 내유성이 우수한 성질을 갖는 엘라스토머)를 블랜드하는 수단이 있으며, 예를 들면 아크릴 고무에 실리콘 고무를 블랜드하고, 과산화물을 가교하는 기술이 알려져 있다.Additionally, as an approach to improving the heat resistance of acrylic rubber, there is a means of blending extreme elastomers (elastomers with excellent heat resistance and oil resistance properties such as fluorocarbon rubber, fluorosilicone rubber, and silicone rubber) with acrylic rubber, for example. For example, a technology is known to blend silicone rubber with acrylic rubber and crosslink it with peroxide.
금속면과의 점착 방지에 대해서는, 아크릴 고무에 에스테르계 왁스, 파라핀계 왁스, 실리콘 오일 등, 내부 이형제의 첨가가 효과적이다. 예를 들면, 롤 점착성의 개량에 대하여, 아크릴 고무에 대하여 분자 내에 메타크릴기를 갖는 실리콘 오일을 첨가하는 기술이 보고되어 있다.To prevent adhesion to metal surfaces, the addition of an internal mold release agent such as ester wax, paraffin wax, or silicone oil to acrylic rubber is effective. For example, a technique for improving roll adhesion by adding silicone oil having a methacryl group in the molecule to acrylic rubber has been reported.
그러나 카르복시기 함유 아크릴 고무에 대하여 어떠한 기재도 없고, 내열성에 대한 효과도 분명하지 않다. 카르복시기 함유 아크릴 고무는 내열성이 우수한 한편, 롤 점착성이 열화되어 이것을 해결하는 방법이 요구되고 있다.However, there is no description of acrylic rubber containing carboxyl groups, and the effect on heat resistance is not clear. Carboxyl group-containing acrylic rubber has excellent heat resistance, but its roll adhesion deteriorates, and a method to solve this problem is required.
또한 내유성, 압축 영구 왜곡성 등을 개량하기 위해 불포화 디카르복실산 모노알킬에스테르 공중합 아크릴계 엘라스토머와, 아민계의 가황제를 조합한 아크릴 고무 조성물도 알려져 있다. 그러나 이 아크릴 고무 조성물은 가황물의 내열성이 불충분하여 개선이 요구되고 있다.Also known are acrylic rubber compositions combining an unsaturated dicarboxylic acid monoalkyl ester copolymerized acrylic elastomer and an amine-based vulcanizing agent to improve oil resistance, compression set, etc. However, the heat resistance of this acrylic rubber composition is insufficient for the vulcanizate, and improvement is required.
본 발명은 상기한 바와 같은 문제점을 해결하기 위해 안출된 것으로,The present invention was created to solve the problems described above,
카르복실기 아크릴 고무로 조성되는 호스 조성물을 개발함으로써 고내열성, 내한성 등의 물성을 향상시킬 수 있는 고내열성 아크릴 탄성소재 조성물을 제공하는 것을 목적으로 한다.The purpose is to provide a highly heat-resistant acrylic elastic material composition that can improve physical properties such as high heat resistance and cold resistance by developing a hose composition composed of carboxyl group acrylic rubber.
본 발명에 따른 고내열성 아크릴 탄성소재 조성물은 CMB(Carbon Master Batch) 및 FMB(Final Master Batch)를 통해 제조되는 내열성 아크릴계 탄성소재 호스 조성물에 있어서, 상기 CMB에서는 아크릴 고무 100 중량부에 대하여 제1 카본필러 30 내지 40 중량부, 제2 카본필러 35 내지 45 중량부, 필러 2.5 내지 7.5 중량부, 가공조제 1 내지 3 중량부, 가소제 5 내지 7 중량부, 노방제 1 내지 3 중량부를 포함하고, 상기 FMB에서는 상기 아크릴 고무 100 중량부에 대하여 가류제 0.4 내지 0.6 중량부, 가류촉진제 0.8 내지 2.7 중량부를 포함하여 이루어진다.The highly heat-resistant acrylic elastic material composition according to the present invention is a heat-resistant acrylic elastic material hose composition manufactured through CMB (Carbon Master Batch) and FMB (Final Master Batch), wherein the CMB contains first carbon relative to 100 parts by weight of acrylic rubber. It contains 30 to 40 parts by weight of filler, 35 to 45 parts by weight of second carbon filler, 2.5 to 7.5 parts by weight of filler, 1 to 3 parts by weight of processing aid, 5 to 7 parts by weight of plasticizer, and 1 to 3 parts by weight of degreasing agent, FMB contains 0.4 to 0.6 parts by weight of a vulcanizing agent and 0.8 to 2.7 parts by weight of a vulcanization accelerator based on 100 parts by weight of the acrylic rubber.
본 발명에 따른 상기 제1 카본필러는 카본블랙 N550, 상기 제2 카본필러는 카본블랙 N330인 것을 특징으로 한다.The first carbon filler according to the present invention is carbon black N550, and the second carbon filler is carbon black N330.
본 발명에 따른 상기 필러는 TAIC(Trially isocyanurate), a hydrous magnesium silicate로 구성되는 것을 특징으로 한다.The filler according to the present invention is characterized in that it is composed of TAIC (Trially isocyanurate), a hydrous magnesium silicate.
본 발명에 따른 상기 가공조제는 상기 아크릴 고무 100 중량부에 대하여 0.5 내지 1.5 중량부의 제1 가공조제와, 0.5 내지 1.5 중량부의 제2 가공조제를 포함하여 이루어지되, 상기 제1 가공조제는 스테아린산(Stearic acid)로 구성되고, 상기 제2 가공조제는 펜타에리트리톨 테트라스테아르산 염(Pentaerythrityl tetrastearate)으로 구성되는 것을 특징으로 한다.The processing aid according to the present invention includes 0.5 to 1.5 parts by weight of a first processing aid and 0.5 to 1.5 parts by weight of a second processing aid based on 100 parts by weight of the acrylic rubber, wherein the first processing aid contains stearic acid ( stearic acid), and the second processing aid is characterized in that it consists of pentaerythrityl tetrastearate.
본 발명에 따른 상기 가소제는 에테르에스테르계로 구성되는 것을 특징으로 한다.The plasticizer according to the present invention is characterized in that it is composed of an ether ester type.
본 발명에 따른 상기 노방제는 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline로 구성되는 것을 특징으로 한다.The anti-oxidant according to the present invention is characterized in that it consists of 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline.
본 발명에 따른 상기 가류제는 4,4'-디아미노디페닐 에테르로 구성되는 것을 특징으로 한다.The curing agent according to the present invention is characterized in that it consists of 4,4'-diaminodiphenyl ether.
본 발명에 따른 상기 가류촉진제는 상기 아크릴 고무 100 중량부에 대하여 0.5 내지 2 중량부의 제1 가류촉진제와, 0.3 내지 0.7 중량부의 제2 가류촉진제를 포함하여 구성되되, 상기 제1 가류촉진제는 디페닐 구아니딘(Diphenyl Guanidine)으로 구성되고, 상기 제2 가류촉진제는 AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, SATURATED DIBASIC ACIDS(Tertiary amine complex)로 구성되는 것을 특징으로 한다.The vulcanization accelerator according to the present invention includes 0.5 to 2 parts by weight of a first vulcanization accelerator and 0.3 to 0.7 parts by weight of a second vulcanization accelerator based on 100 parts by weight of the acrylic rubber, wherein the first vulcanization accelerator is diphenyl. It is composed of guanidine (Diphenyl Guanidine), and the second vulcanization accelerator is composed of AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, and SATURATED DIBASIC ACIDS (Tertiary amine complex).
본 발명에 따른 고내열성 아크릴 탄성소재 조성물은 카르복실기 아크릴 고무로 조성되는 호스 조성물을 개발하고, 개발된 호스 조성물에 대한 소재 내열성, 제품내열성, 내유성, 압축영구 줄음율, 내오존성 등의 물성 평가를 통해 제품의 신뢰성을 담보할 수 있다.The highly heat-resistant acrylic elastic material composition according to the present invention was developed by developing a hose composition composed of carboxyl group acrylic rubber, and evaluating the physical properties of the developed hose composition such as material heat resistance, product heat resistance, oil resistance, compression set rate, and ozone resistance. The reliability of the product can be guaranteed.
또한 본 발명은 기존에 대외 수입에 의존하던 소재를 동등 또는 그 이상을 물성을 갖는 소재를 개발하여 국산화함으로써 경제성을 물론이고, 글로벌 경쟁에서 보다 효과적으로 대응할 수 있는 토대를 마련할 수 있다.In addition, the present invention develops and domestically produces materials with physical properties equal to or higher than those previously dependent on foreign imports, thereby laying the foundation for not only economic feasibility but also a more effective response to global competition.
도 1 및 도 2는 본 발명에 따른 고내열성 아크릴 탄성소재의 제작공정을 나타내는 공정도,
도 3은 본 발명에 따른 고내열성 아크릴 탄성소재와 현 양산품의 Heat loss, Ash, MV를 나타내는 비교례,
도 4는 본 발명에 따른 고내열성 아크릴 탄성소재를 이용한 양산 평가 제품과, 표면 상태를 나타내는 비교례,
도 5 및 도 6은 본 발명에 따른 고내열성 아크릴 탄성소재에 대한 시험성적서.1 and 2 are process charts showing the manufacturing process of the highly heat-resistant acrylic elastic material according to the present invention;
Figure 3 is a comparative example showing heat loss, Ash, and MV of the highly heat-resistant acrylic elastic material according to the present invention and current mass-produced products;
Figure 4 is a comparative example showing the mass production evaluation product using the highly heat-resistant acrylic elastic material according to the present invention and the surface condition;
Figures 5 and 6 are test reports for the highly heat-resistant acrylic elastic material according to the present invention.
본명과 본 발명의 동작상의 이점 및 본 발명의 실시에 의하여 달성되는 목적을 설명하기 위하여 이하에서는 본 발명의 바람직한 실시례를 예시하고 이를 참조하여 살펴본다.In order to explain the present invention, the operational advantages of the present invention, and the purpose achieved by practicing the present invention, preferred embodiments of the present invention will be exemplified and examined with reference to them.
먼저, 본 출원에서 사용한 용어는 단지 특정한 실시례를 설명하기 위해 사용된 것으로서, 본 발명을 한정하려는 의도가 아니며, 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함할 수 있다. 또한 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.First, the terms used in this application are only used to describe specific embodiments and are not intended to limit the present invention, and singular expressions may include plural expressions unless the context clearly indicates otherwise. In addition, in the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other It should be understood that this does not exclude in advance the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof.
본 발명을 설명함에 있어서, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.
도 1 내지 도 3에 도시된 바와 같이 본 발명에 따른 고내열성 아크릴계 탄성소재 조성물은 CMB(Carbon Master Batch) 공정에서 원료 고무, 즉 아크릴 고무와 카본, 오일, 보강제 등의 배합제 혼련을 통해 반제품 상태의 배합고무를 제조한다.As shown in Figures 1 to 3, the highly heat-resistant acrylic elastic material composition according to the present invention is in a semi-finished state through mixing raw rubber, that is, acrylic rubber, with a compounding agent such as carbon, oil, and reinforcing agent in the CMB (Carbon Master Batch) process. Manufactures compounded rubber.
이 후 FMB(Final Master Batch) 공정에서는 CMB 단계의 배합고무에 가류제, 가류촉진제 등을 첨가하여 가류가 될 수 있는 고무를 제조하게 된다.Afterwards, in the FMB (Final Master Batch) process, vulcanizing agents and vulcanizing accelerators are added to the compounded rubber of the CMB stage to produce rubber that can be vulcanized.
도 1에 도시된 바와 같이 CMB 공정은 원자재 보관으로부터, C/B Oil 개량, 약품 개량, 폴리머 개량, CMB 혼련 및 냉각/건조 순으로 진행될 수 있다.As shown in Figure 1, the CMB process can proceed in the following order: raw material storage, C/B Oil improvement, chemical improvement, polymer improvement, CMB mixing, and cooling/drying.
CMB 공정을 통해 제조된 반제품 상태의 배합고무를 가류 가능한 고무로 제조하기 위한 FMB 공정은 도 2에 도시된 바와 같이 CMB 숙성, FMB 혼련, 블랜딩, 스트립 성형, 냉각/건조 및 계량/포장 순으로 진행될 수 있다.The FMB process for manufacturing semi-finished compound rubber manufactured through the CMB process into vulcanizable rubber proceeds in the following order: CMB aging, FMB kneading, blending, strip forming, cooling/drying, and weighing/packaging, as shown in Figure 2. You can.
먼저 CMB 단계에서 배합고무 조성비는 원료 고무, 즉 아크릴 고무 ,제1 카본필러, 제2 카본필러, 필러, 가공조제, 가소제 및 노방제 등의 배합제를 혼련하여 반제품 상태의 배합고무를 조제하게 된다.First, in the CMB stage, the composition ratio of the compounded rubber is mixed with the raw rubber, that is, acrylic rubber, first carbon filler, second carbon filler, filler, processing aid, plasticizer, and preservative, etc. to prepare semi-finished compound rubber. .
다음으로 FMB 단계에서는 CMB 상태의 배합고무에 가류제 및 가류촉진제를 첨가하여 가류 가능한 고무를 제조하게 된다.Next, in the FMB stage, a vulcanizing agent and a vulcanizing accelerator are added to the CMB compound rubber to produce vulcanizable rubber.
본 발명에 따른 고내열성 아크릴 탄성고무 조성물은 원료고무, 아크릴 고무, 보강제 및 첨가제의 최적 비율을 선정하기 위해 표 1과 같이 비교예를 제시하고, 표 2에 따른 물성 시험을 통해 최종적으로 예시 6에 따른 최적의 배합비율을 선정하였다.The highly heat-resistant acrylic elastomeric rubber composition according to the present invention presents a comparative example as shown in Table 1 to select the optimal ratio of raw rubber, acrylic rubber, reinforcing agent, and additives, and finally shows Example 6 through physical property tests according to Table 2. The optimal mixing ratio was selected.
여기서 표 1의 예시는 대상제품으로 인터쿨러 호스(HMC 규격 MS263-45 Type B)를 바탕으로 예시 1에서 예시 6까지 선정 하였으며, 보다 구체적으로 예시 1 내지 예시 3은 카르복실기 아크릴 고무와 카르복실기 PA-526를 소정 비율로 혼합하였고, 예시 4 내지 예시 6은 카르복실기 아크릴 고무만으로 구성하였다. 또한 예시 1 내지 예시 3, 예시 6은 필러는 첨가하였고, 예시 4 및 예시 5는 필러를 첨가하지 않았다.Here, the examples in Table 1 were selected from Example 1 to Example 6 based on the intercooler hose (HMC standard MS263-45 Type B) as the target product. More specifically, Examples 1 to 3 were selected using carboxyl acrylic rubber and carboxyl group PA-526. It was mixed in a predetermined ratio, and Examples 4 to 6 were composed only of carboxyl group acrylic rubber. Additionally, filler was added in Examples 1 to 3 and Example 6, and no filler was added in Examples 4 and 5.
표 1에 따른 예시 1에서 예시 6에 대한 물성의 평가결과는 표 2와 같다.The evaluation results of physical properties for Examples 1 to 6 according to Table 1 are shown in Table 2.
즉 주요 평가 항목으로 미가황 물성 부문에서는 Rheometer, Mooney viscometer(121℃), 2차 가류상태 물성 시험(180℃×2Hr), 대상제품인 인터쿨러 호스 환경적으로 요구되어지는 특성인 노화성(185℃×168Hr), 내유성(185℃×2Hr×ENG OIL), 내 Blow by Gas A법(40℃×168Hr×E20:ENG OIL=5:95), 내 Blow by Gas B법(40℃×168Hr×M15:ENG OIL=5:95), 내 Blow by Gas C법(40℃×168Hr×Fuel D:ENG OIL=5:95), 압축 줄음률 시험(온도×22Hr) 및 내오존성 시험(40℃×72Hr×20%×100pphm) 등을 통한 물성 시험을 수행하였다.In other words, the main evaluation items are Rheometer and Mooney viscometer (121℃) in the unvulcanized physical properties section, secondary vulcanized state physical property test (180℃ 168Hr), oil resistance (185℃×2Hr×ENG OIL), Blow by Gas A method (40℃×168Hr×E20:ENG OIL=5:95), Blow by Gas B method (40℃×168Hr×M15: ENG OIL=5:95), Blow by Gas C method (40℃×168Hr×Fuel D:ENG OIL=5:95), compression shrinkage test (temperature×22Hr) and ozone resistance test (40℃×72Hr× Physical property tests were performed using 20% × 100 pphm).
상기 물성 시험을 통해 확인할 수 있는 바와 같이 예시 6이 모든 시험에 따른 기준치를 만족하는 것으로 확인되었으며, 특히 고객 요구 물성 및 흐름성을 검토 결과 예시 6안이 양산재질로 가장 적합한 것으로 판명되어 최종적인 최적의 배합조성물로 선정하였다.As can be confirmed through the above physical property test, it was confirmed that Example 6 satisfies the standard values according to all tests. In particular, as a result of reviewing the customer-required physical properties and flowability, Example 6 was found to be the most suitable as a mass production material, and was ultimately selected as the optimal material. It was selected as a blended composition.
상기 표 1 및 표 2에 따라 선정된 본 발명에 따른 아크릴 탄성소재에서 아크릴 고무와 첨가제 등의 조성비는 다음과 같다.The composition ratio of acrylic rubber and additives in the acrylic elastic material according to the present invention selected according to Tables 1 and 2 above is as follows.
먼저 CMB 단계에서 배합고무 조성비는 원료 고무, 즉 아크릴 고무 100 중량부에 대하여 제1 카본필러 30 내지 40 중량부, 제2 카본필러 35 내지 45 중량부, 필러 2.5 내지 7.5 중량부, 가공조제 1 내지 3 중량부, 가소제 5 내지 7 중량부, 노방제 1 내지 3 중량부 등의 배합제를 혼련하여 반제품 상태의 배합고무를 조제하게 된다.First, in the CMB stage, the compounded rubber composition ratio is 30 to 40 parts by weight of the first carbon filler, 35 to 45 parts by weight of the second carbon filler, 2.5 to 7.5 parts by weight of filler, and 1 to 1 to 1 part of processing aid based on 100 parts by weight of raw rubber, that is, acrylic rubber. Mixing agents such as 3 parts by weight, 5 to 7 parts by weight of plasticizer, and 1 to 3 parts by weight of degreasing agent are mixed to prepare compound rubber in a semi-finished product state.
바람직하게는 제1 카본블랙은 35 중량부, 제2 카본블랙은 40 중량부, 필러는 5 중량부, 가공제조(제1 가공조제 및 제2 가공조제 포함)는 2 중량부, 가소제는 6 중량부, 노방제는 2 중량부로 조성될 수 있다.Preferably, the first carbon black is 35 parts by weight, the second carbon black is 40 parts by weight, the filler is 5 parts by weight, the processing agent (including the first processing aid and the second processing aid) is 2 parts by weight, and the plasticizer is 6 parts by weight. Part, the anti-corrosion agent may be composed of 2 parts by weight.
다음으로 FMB 단계에서는 아크릴 고무 100 중량부에 대하여 가류제 0.4 내지 0.6 중량부, 가류촉진제 0.8 내지 2.7 중량부를 첨가하여 가류 가능한 고무를 제조하게 된다.Next, in the FMB step, 0.4 to 0.6 parts by weight of a vulcanizing agent and 0.8 to 2.7 parts by weight of a vulcanization accelerator are added to 100 parts by weight of acrylic rubber to produce a vulcanizable rubber.
바람직하게는 가류제는 0.5 중량부 및 가류촉진제(제1 가류촉진제 및 제2 가류촉진제 포함)는 1.5 중량부로 조성될 수 있다.Preferably, the vulcanizing agent may be comprised of 0.5 parts by weight and the vulcanization accelerator (including the first and second vulcanization accelerators) may be comprised of 1.5 parts by weight.
본 발명에 따른 제1 카본필러는 카본블랙 N550(FEF), 제2 카본필러는 카본블랙 N330(HAF)으로 구성되는 것이 바람직하다. 제1 카본필러인 N550(FEF)는 압출시 수축변형이 작고, 평활한 표면을 얻을 수 있으며, 발열이 낮고 열전도가 양호하며, Modulus는 N330과 동일한 수준이다. 제2 카본블랙인 N330(HAF)은 적당한 보강성, 인장강도, Modulus, 신장률이 우수하고, 물성 밸런스가 우수하다. 이와 같은 제1 카본필러는 아크릴 고무 100중량부에 대하여 30 내지 40 중량부, 제2 카본필러는 아크릴 고무 100중량부에 대하여 35 내지 45 중량부 범위 내에서 첨가되는 것이 바람직하다.The first carbon filler according to the present invention is preferably composed of carbon black N550 (FEF), and the second carbon filler is preferably composed of carbon black N330 (HAF). N550 (FEF), the first carbon filler, has small shrinkage deformation during extrusion, can obtain a smooth surface, has low heat generation and good heat conduction, and its modulus is at the same level as N330. The second carbon black, N330 (HAF), has moderate reinforcement properties, excellent tensile strength, modulus, and elongation, and has excellent physical property balance. The first carbon filler is preferably added in an amount of 30 to 40 parts by weight based on 100 parts by weight of acrylic rubber, and the second carbon filler is preferably added in an amount of 35 to 45 parts by weight based on 100 parts by weight of acrylic rubber.
본 발명에 따른 필러는 Talc(hydrous magnesium silicate), 즉 수소마그네슘규산염으로 구성되는 것이 바람직하다. 수소마그네슘규산염은 활성 표면이 매우 크고, 철 함량이 적고 무색으로 매우 부드럽고 촉감이 매끄러우면서 전기에 대한 절연성을 갖는다. 이러한 필러는 아크릴 고무 100중량부에 대하여 2.5 내지 7.5 중량부 범위 내에서 첨가되는 것이 바람직하다.The filler according to the present invention is preferably composed of Talc (hydrous magnesium silicate), that is, hydrogen magnesium silicate. Hydrogen magnesium silicate has a very large active surface, has a low iron content, is colorless, is very soft and smooth to the touch, and has electrical insulating properties. This filler is preferably added in the range of 2.5 to 7.5 parts by weight based on 100 parts by weight of acrylic rubber.
본 발명에 따른 가공조제는 아크릴 고무 100 중량부에 대하여 0.5 내지 1.5 중량부의 제1 가공조제와, 0.5 내지 1.5 중량부의 제2 가공조제를 포함하여 구성된다.The processing aid according to the present invention includes 0.5 to 1.5 parts by weight of a first processing aid and 0.5 to 1.5 parts by weight of a second processing aid based on 100 parts by weight of acrylic rubber.
여기서 제1 가공조제는 스테아린산(Stearic acid)로 구성되고, 제2 가공조제는 펜타에리트리톨 테트라스테아르산 염(Pentaerythrityl tetrastearate)으로 구성되는 것이 바람직하다. 이 경우 제1 및 제2 가공조제인 고무 가공 시 무니점도(Mooney viscosity)의 감소, 블렌딩의 균질화, 믹싱시간 단축, 분산성 향상 효과를 높일 수 있다.Here, the first processing aid is preferably composed of stearic acid, and the second processing aid is preferably composed of pentaerythrityl tetrastearate. In this case, the first and second processing aids can increase the effects of reducing Mooney viscosity, homogenizing blending, shortening mixing time, and improving dispersibility during rubber processing.
본 발명에 따른 가소제는 에테르에스테르계로 구성되는데, 에테르에스테르계 가소제는 신율, 인장강도, 내충격성 등의 기계적 물성을 향상시켜 수지와 상용성을 높일 수 있고, 열안전성, 유연성, 점착성, 내한성이 좋고, 특히 가공온도범위가 넓을 뿐만 아니라, 블리드 아웃(bleed out) 현상이 발생하지 않으며, 내구성이 뛰어나다. 이러한 가소제는 아크릴 고무 100중량부에 대하여 5 내지 7 중량부 범위 내에서 배합되는 것이 바람직하다.The plasticizer according to the present invention is composed of an ether ester type. The ether ester plasticizer can increase compatibility with the resin by improving mechanical properties such as elongation, tensile strength, and impact resistance, and has good thermal stability, flexibility, adhesion, and cold resistance. In particular, not only is the processing temperature range wide, the bleed out phenomenon does not occur, and durability is excellent. These plasticizers are preferably mixed in the range of 5 to 7 parts by weight based on 100 parts by weight of acrylic rubber.
본 발명에 따른 노방제는 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline로 구성되는 것이 바람직하다. 이러한 노방제는 아크릴 고무 100중량부에 대하여 1 내지 3 중량부 범위 내에서 첨가되는 것이 바람직하다.The anti-oxidant according to the present invention is preferably composed of 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline. It is preferable that this anti-corrosion agent is added in the range of 1 to 3 parts by weight based on 100 parts by weight of acrylic rubber.
본 발명에 따른 가류제는 4,4'-디아미노디페닐 에테르로 구성될 수 있고, 아크릴 고무 100 중량부에 대하여 0.4 내지 0.6 중량부 범위 내에서 첨가되는 것이 바람직하다.The curing agent according to the present invention may be composed of 4,4'-diaminodiphenyl ether, and is preferably added in the range of 0.4 to 0.6 parts by weight based on 100 parts by weight of acrylic rubber.
본 발명에 따른 가류촉진제는 상기 아크릴 고무 100 중량부에 대하여 0.5 내지 2 중량부의 제1 가류촉진제와, 0.3 내지 0.7 중량부의 제2 가류촉진제를 포함하여 구성되되, 제1 가류촉진제는 디페닐 구아니딘(Diphenyl Guanidine)으로 구성되고, 제2 가류촉진제는 AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, SATURATED DIBASIC ACIDS(Tertiary amine complex)로 구성되는 것이 바람직하다.The vulcanization accelerator according to the present invention includes 0.5 to 2 parts by weight of a first vulcanization accelerator and 0.3 to 0.7 parts by weight of a second vulcanization accelerator based on 100 parts by weight of the acrylic rubber, wherein the first vulcanization accelerator is diphenyl guanidine ( Diphenyl Guanidine), and the second vulcanization accelerator is preferably composed of AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, SATURATED DIBASIC ACIDS (Tertiary amine complex).
본 발명에 따른 아크릴 탄성소재(카르복실계)를 기준으로 최적 배합비를 선정하였으며, 도 3은 이러한 아크릴 탄성소재와 양산품에 대한 Htea loss, Ash, Mv 검증하였으며, 검증 결과 양산품인 유니마텍 NOK社 Polymer(PA-526) 대비 무늬 점도가 소폭 저감된 것을 확인할 수 있다. 여기서 적용 제품은 인터쿨러 호스로 선정하였다.The optimal mixing ratio was selected based on the acrylic elastic material (carboxylic type) according to the present invention, and Figure 3 shows Htea loss, Ash, and Mv for this acrylic elastic material and mass-produced products. As a result of the verification, the mass-produced product, Unimatec NOK Polymer (PA-526) It can be seen that the contrast pattern viscosity has decreased slightly. Here, the applied product was selected as an intercooler hose.
이하에서는 상기한 바와 같은 배합비를 갖는 아크릴 탄성소재에 대한 물성 평가 결과를 설명하기로 한다. 이러한 물성평가는 LAB 평가와, 양산 평가를 통해 검증하였다.Hereinafter, the physical property evaluation results for the acrylic elastic material having the above-mentioned mixing ratio will be described. These physical property evaluations were verified through LAB evaluation and mass production evaluation.
아래 표 3는 고내열성 아크릴 탄성소재 적용 컴파운드 미가황 물성검증 및 점도를 비교한 결과이다.Table 3 below shows the results of verification of unvulcanized physical properties and comparison of viscosity of compounds using highly heat-resistant acrylic elastic materials.
현 양산품 대비 무늬 점도가 #P-3I(본 발명에 따른 고내열성 아크릴 탄성소재)에서 유사 수준인 것으로 확인되어 양산 평가 시료로 결정하였다.The pattern viscosity compared to the current mass-produced product was confirmed to be at a similar level in #P-3I (high heat-resistant acrylic elastic material according to the present invention), so it was decided as a mass-produced evaluation sample.
비교군 유니마텍 ACM은 PA-526로 카르복실계 아크릴 고무를 선정하였고, 이 경우 #P-3I의 LAB 평가 및 양산 평가에서 모두 경도를 증가시켰다.Unimatec ACM, the comparative group, selected a carboxylic acrylic rubber as PA-526, and in this case, hardness was increased in both LAB evaluation and mass production evaluation of #P-3I.
평가 제품은 LAB 평가 및 양산 평가 모두에서 인터쿨러용 호스 제품으로 제작 및 평가였다.The evaluation product was manufactured and evaluated as an intercooler hose product in both LAB evaluation and mass production evaluation.
이 경우 LAB 평가 시, 유니마텍 ACM(아크릴 고무와 P-526(카르복실계) 배합_예시 1 내지 예시 3)를 비교군으로 하였고, 시험 년차별로 1차 년도에는 #P-2I, 2차 년도에는 #P-3I 제품으로 검증 후, 양산품 유사 기준의 Mooney Viscosity 값을 확인 하였으며, Rheometer 측정을 통하여 가류 여부를 검증 하였다.In this case, when evaluating LAB, Unimatec ACM (mixture of acrylic rubber and P-526 (carboxyl type)_Example 1 to Example 3) was used as a comparison group, and by test year, #P-2I in the first year and #P-2I in the second year. After verification with the #P-3I product, the Mooney Viscosity value of similar standards to mass-produced products was confirmed, and vulcanization was verified through rheometer measurement.
표 4는 본 발명에 따른 고내열성 아크릴 탄성소재 적용 컴파운드 기본 물성에 대한 평가 결과이다.Table 4 shows the evaluation results of the basic physical properties of the compound using the highly heat-resistant acrylic elastic material according to the present invention.
검증 결과 LAB 및 양산 물성 평가시 정량적 목표, 특히 인장강도를 8.0Min 기준 대비 만족하고 있는 것을 확인할 수 있고, 또한 유니마텍 ACM(비교군) 대비하여 LAB 평가 및 양산 평가 모두 증가되는 것을 확인할 수 있다. As a result of the verification, it can be confirmed that the quantitative goals, especially tensile strength, are satisfied compared to the 8.0Min standard when evaluating LAB and mass production properties, and it can also be confirmed that both LAB evaluation and mass production evaluation are increased compared to Unimatec ACM (comparison group).
표 5는 본 발명에 따른 고내열성 아크릴계 탄성소재 적용 컴파운드 물성평가에 대한 평가 결과이다.Table 5 shows the evaluation results of the physical property evaluation of the compound applied with the highly heat-resistant acrylic elastic material according to the present invention.
정량적 물성 평가 기준으로 소재 내열서, 제품내열성, 내유성, 압축영구 줄음율, 내오존성 평가 결과 정량적 목표를 만족하는 것을 확인할 수 있다.As a standard for quantitative physical property evaluation, it can be confirmed that the quantitative goals are met as a result of the evaluation of material heat resistance, product heat resistance, oil resistance, compression set, and ozone resistance.
아울러 본 발명에 따른 고내열성 아크릴 탄성소재에 대한 자체 물성 평가를 공인받기 위해 도 5 및 도 6과 같이 물성 성적서를 통해 검증하였다.In addition, in order to obtain official evaluation of the physical properties of the highly heat-resistant acrylic elastic material according to the present invention, it was verified through physical property reports as shown in FIGS. 5 and 6.
적용 제품은 인터쿨러용 호스이고, 도 5는 기존품과 본 발명에 따른 아크릴 탄성소재로 제작된 호스 단품열노화시험에 대한 검증서이다. 여기서 국부적인 부풀음과 공기누설이 없고, 파열강도(기준 600Mpa 이상) 기준을 만족하였고, 외경변화율 역시 기준치(0 ~ 10%)를 만족하였다.The applied product is a hose for an intercooler, and Figure 5 is a verification document for the heat aging test of a single hose made of an acrylic elastic material according to the existing product and the present invention. Here, there was no local swelling or air leakage, the bursting strength standard (standard 600Mpa or more) was satisfied, and the outer diameter change rate also met the standard value (0 to 10%).
또한 도 6은 호스 단품내구시험에 대한 검증서이고, 국부적인 부풀음, 공기누설이 없음을 확인하였다.In addition, Figure 6 is a verification document for the durability test of a single hose, and it was confirmed that there was no local swelling or air leakage.
도 4는 Inter Cooler(#P-3I)를 압출/가류를 통해 제작 시, 제품 표면 상태가 양호한 것을 확인할 수 있다.Figure 4 shows that the product surface condition is good when the Inter Cooler (#P-3I) is manufactured through extrusion/vulcanization.
이와 같이 본 발명은 도면에 도시된 일실시례를 참고로 설명되었으나, 이는 예시적인 것에 불과하며, 본 기술 분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시례가 가능하다는 점을 이해할 것이다.As such, the present invention has been described with reference to an embodiment shown in the drawings, but this is merely illustrative, and various modifications and other equivalent embodiments can be made by those skilled in the art. You will understand.
따라서 본 발명의 진정한 기술적 보호범위는 첨부된 청구범위의 기술적 사상에 의해 정해져야 할 것이다.Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the attached claims.
Claims (8)
상기 CMB에서는 아크릴 고무 100 중량부에 대하여 제1 카본필러 30 내지 40 중량부, 제2 카본필러 35 내지 45 중량부, 필러 2.5 내지 7.5 중량부, 가공조제 1 내지 3 중량부, 가소제 5 내지 7 중량부, 노방제 1 내지 3 중량부를 포함하고,
상기 FMB에서는 상기 아크릴 고무 100 중량부에 대하여 가류제 0.4 내지 0.6 중량부, 가류촉진제 0.8 내지 2.7 중량부를 포함하여 이루어지되,
상기 제1 카본필러는 카본블랙 N550, 상기 제2 카본필러는 카본블랙 N330이고,
상기 필러는 Talc(hydrous magnesium silicate)로 구성되며,
상기 가공조제는 상기 아크릴 고무 100 중량부에 대하여 0.5 내지 1.5 중량부의 제1 가공조제와, 0.5 내지 1.5 중량부의 제2 가공조제를 포함하여 이루어지되,
상기 제1 가공조제는 스테아린산(Stearic acid)로 구성되고, 상기 제2 가공조제는 펜타에리트리톨 테트라스테아르산 염(Pentaerythrityl tetrastearate)으로 구성되고,
상기 가소제는 에테르에스테르계로 구성되며,
상기 노방제는 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline로 구성되고,
상기 가류제는 4,4'-디아미노디페닐 에테르로 구성되며,
상기 가류촉진제는 상기 아크릴 고무 100 중량부에 대하여 0.5 내지 2 중량부의 제1 가류촉진제와, 0.3 내지 0.7 중량부의 제2 가류촉진제를 포함하여 구성되되,
상기 제1 가류촉진제는 디페닐 구아니딘(Diphenyl Guanidine)으로 구성되고,
상기 제2 가류촉진제는 AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, SATURATED DIBASIC ACIDS(Tertiary amine complex)로 구성되는 것을 특징으로 하는 고내열성 아크릴 탄성소재 조성물.In the heat-resistant acrylic elastic material hose composition manufactured through CMB (Carbon Master Batch) and FMB (Final Master Batch),
In the CMB, 30 to 40 parts by weight of the first carbon filler, 35 to 45 parts by weight of the second carbon filler, 2.5 to 7.5 parts by weight of the filler, 1 to 3 parts by weight of the processing aid, and 5 to 7 parts by weight of the plasticizer, based on 100 parts by weight of acrylic rubber. 1 to 3 parts by weight of a preservative,
The FMB includes 0.4 to 0.6 parts by weight of a vulcanizing agent and 0.8 to 2.7 parts by weight of a vulcanization accelerator based on 100 parts by weight of the acrylic rubber,
The first carbon filler is carbon black N550, and the second carbon filler is carbon black N330,
The filler is composed of Talc (hydrous magnesium silicate),
The processing aid includes 0.5 to 1.5 parts by weight of a first processing aid and 0.5 to 1.5 parts by weight of a second processing aid based on 100 parts by weight of the acrylic rubber,
The first processing aid consists of stearic acid, and the second processing aid consists of pentaerythrityl tetrastearate,
The plasticizer is composed of ether ester type,
The preservative is composed of 4-(1-methyl-1-phenylethyl)-N-[4-(1-methyl-1-phenylethyl)phenyl]aniline,
The curing agent consists of 4,4'-diaminodiphenyl ether,
The vulcanization accelerator includes 0.5 to 2 parts by weight of a first vulcanization accelerator and 0.3 to 0.7 parts by weight of a second vulcanization accelerator based on 100 parts by weight of the acrylic rubber,
The first vulcanization accelerator consists of diphenyl guanidine,
The second vulcanization accelerator is a highly heat-resistant acrylic elastic material composition, characterized in that it consists of AMPORPHOUS SILICA, 1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE, and SATURATED DIBASIC ACIDS (Tertiary amine complex).
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