KR20130035033A - Adhesives composite for adhereing low-acn nbr and adhesives solution for adhereing low-acn nbr - Google Patents
Adhesives composite for adhereing low-acn nbr and adhesives solution for adhereing low-acn nbr Download PDFInfo
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- KR20130035033A KR20130035033A KR1020110099247A KR20110099247A KR20130035033A KR 20130035033 A KR20130035033 A KR 20130035033A KR 1020110099247 A KR1020110099247 A KR 1020110099247A KR 20110099247 A KR20110099247 A KR 20110099247A KR 20130035033 A KR20130035033 A KR 20130035033A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title 1
- 229920001971 elastomer Polymers 0.000 claims abstract description 115
- 239000005060 rubber Substances 0.000 claims abstract description 115
- 150000002825 nitriles Chemical class 0.000 claims abstract description 38
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 61
- 239000003921 oil Substances 0.000 description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 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
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UZZHPCNDHCAKNU-UHFFFAOYSA-N N-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1(CCCCC1)NSC=1SC2=C(N1)C=CC=C2.C2(CCCCC2)NSC=2SC1=C(N2)C=CC=C1 UZZHPCNDHCAKNU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 중/저 니트릴NBR 고무 접착용 접착제 조성물 및 /저 니트릴 NBR 고무 접착용 접착제 용액을 개시한다. 본 발명의 실시예에 따른 중/저 니트릴 NBR 고무 접착용 접착제 조성물은, ACN 함량이 30mol%이하인 중/저니트릴 NBR 고무와 금속 사이에 개재되어서, 상기 중/저니트릴 NBR 고무를 상기 금속에 접착시키는 접착제의 조성물로서, 페놀 수지와, NBR 고무와, CPE(Chlorinated Polyethylene)고무를 폴리머로 하며, 상기 접착제의 30 내지 70 중량부를 가지는 NBR/CPE 고무 원료를 포함한다. The present invention discloses a low / low nitrile NBR rubber adhesive composition and a low / low nitrile NBR rubber adhesive solution. The adhesive composition for medium / low nitrile NBR rubber adhesive according to an embodiment of the present invention is interposed between the medium / low nitrile NBR rubber having an ACN content of 30 mol% or less and the metal, thereby adhering the medium / low nitrile NBR rubber to the metal. The adhesive composition to be used includes a phenol resin, NBR rubber, and CPE (Chlorinated Polyethylene) rubber as a polymer, and an NBR / CPE rubber raw material having 30 to 70 parts by weight of the adhesive.
Description
본 발명은 중/저니트릴 고무를 접착하는 접착제에 관한 것으로, 보다 상세하게는 차량의 쇽 업소버 씰, 허브 베어링씰, 더스트 씰 등의 아크릴로 니트릴(ACN]함량이 30mol% 이하인 NBR 고무가 적용되는 분야에서, 상기 NBR 고무를 금속에 결합시키는 중/저니트릴 고무 접착용 접착제 조성물 및 중/저 니트릴 NBR 고무 접착용 접착제 용액에 관한 것이다. The present invention relates to an adhesive for adhering medium and low nitrile rubber, and more particularly, NBR rubber having an acrylonitrile (ACN) content of 30 mol% or less, such as a shock absorber seal, a hub bearing seal, a dust seal, of a vehicle, is applied. In the field, the present invention relates to an adhesive composition for medium / low nitrile rubber adhesion and an adhesive solution for medium / low nitrile NBR rubber bonding the NBR rubber to a metal.
차량에 포함된 오일씰의 경우 차량내부의 오일이 외부로 누출되는 것을 방지하고 외부의 먼지가 내부로 유입되는 것을 방지한다. 생활가전 또는 공장에 사용되는 오일씰 또한 마찬가지 기능을 한다. In the case of the oil seal included in the vehicle, it prevents the oil inside the vehicle from leaking to the outside and prevents the dust from entering the inside. The oil seals used in home appliances or factories do the same.
상기 오일씰의 상기 기능을 담당하는 소재는 고무이다. 그런데 상대부에 장착/고정되어 기능을 발휘하기 위해서는 고무만으로는 형상을 유지할 수 없으므로 고무 내부에 금속 제품이 들어가서 고무와 결합을 형성하게 된다. 이 고무와 금속과의 결합에 접착제가 사용되며, 통상적으로 수지계 접착제 또는 고무계 접착제가 많이 사용된다.The material in charge of the function of the oil seal is rubber. However, since the rubber alone cannot maintain its shape in order to be mounted / fixed to the counterpart, the metal product enters the rubber to form a bond with the rubber. An adhesive agent is used for bonding this rubber | gum with a metal, and resin resin adhesive or rubber adhesive agent is used normally.
상기 오일씰 중 아크릴로니트릴부타디엔 고무(NBR)는 우수한 내유성과, 기계적 물성치, 저온 유지성이 우수하여서, 예를 들어 쇼크 압소버 씰(Shock Absorber Seal)이나 허브 베어링 씰(Hub Bearing Seal), 더스트 씰(Dust Seal) 등에 사용된다. Among the oil seals, acrylonitrile butadiene rubber (NBR) is excellent in oil resistance, mechanical properties, and low temperature retention, for example, a shock absorber seal, a hub bearing seal, a dust seal ( Dust seal).
상기 NBR 고무는 ACN(Acrylonitrile) 함량에 따라 18~24%의 저니트릴, 25~30%의 중저니트릴, 31~35% 중니트릴, 36~42%의 고니트릴, 43~48%의 초고니트릴로 분류할 수 있는데, 수지계 접착제의 경우 내열/내유성 등이 좋으나 중/저니트릴 NBR에 사용할 경우에 접착이 힘들다.The NBR rubber is 18-24% low nitrile, 25-30% medium low nitrile, 31-35% heavy nitrile, 36-42% high nitrile, 43-48% ultra high nitrile, depending on ACN (Acrylonitrile) content. In the case of resin-based adhesives, heat / oil resistance is good, but when used in medium / low nitrile NBR, adhesion is difficult.
한편, 고무계 접착제를 사용하여 중/저니트릴 NBR 고무를 접착시킬 경우, 접착력은 양호하나, 수지계 접착제 대비 부족한 내열/내유성에 의해 탈락된 접착제 피막이 상대유의 흐름을 방해할 수 있어 사용에 문제가 된다. 또한 고무계 접착제는 통상적으로 극성 고분자인 염화 고무를 기본으로 한 접착제이기 때문에 접착제를 도포한 후 고온에서 베이킹(baking) 할 수 없어 상온 또는 70℃ 부근에서 건조 수준의 처리를 하므로 180℃정도의 성형 금형에 투입 후 고무와의 접착이 일어나기 전에 접착제가 금형에 녹아내려 금형을 오염시킨다는 단점을 가지고 있다. 따라서 금형 세척을 자주 하여야 하며 오염된 금형 표면에 의하여 제품외관을 오염시켜 상품으로서의 가치를 하락 시키게 된다.On the other hand, when the medium / low nitrile NBR rubber is bonded using a rubber adhesive, the adhesive strength is good, but the adhesive film peeled off due to the heat / oil resistance that is insufficient compared to the resin adhesive can interfere with the flow of the relative oil is a problem in use. In addition, since the rubber adhesive is usually an adhesive based on chlorinated rubber, which is a polar polymer, it cannot be baked at a high temperature after the adhesive is applied, and thus a drying mold is processed at room temperature or around 70 ° C, so that a molding die of about 180 ° C is used. The adhesive has a disadvantage that the adhesive melts into the mold and contaminates the mold after adhesion to the rubber. Therefore, mold cleaning should be done frequently, and contaminated product appearance by contaminated mold surface reduces the value as a commodity.
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, ACN 함량이 30mol%이하인 중/저니트릴 NBR 고무를 금속에 접착함에 있어서, 양호한 접착력을 가지는 동시에, 내유성 및 내열성이 우수한 중/저 니트릴 NBR 고무 접착용 접착제 조성물 및 중/저 니트릴 NBR 고무 접착용 접착제 용액을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above problems, and in bonding medium / low nitrile NBR rubber having an ACN content of 30 mol% or less to a metal, it has a good adhesive force, and is excellent in oil resistance and heat resistance. It is an object to provide an adhesive adhesive composition and an adhesive solution for medium / low nitrile NBR rubber adhesive.
상기 목적을 해결하기 위하여, 본 발명의 실시예에 따른 중/저 니트릴 NBR 고무 접착용 접착제 조성물은, ACN 함량이 30mol%이하인 중/저니트릴 NBR 고무와 금속 사이에 개재되어서, 상기 중/저니트릴 NBR 고무를 상기 금속에 접착시키는 접착제의 조성물로서, 페놀 수지와, NBR 고무와, CPE(Chlorinated Polyethylene)고무를 폴리머로 하며, 상기 접착제의 30 내지 70 중량부를 가지는 NBR/CPE 고무 원료를 포함한다. In order to solve the above object, the adhesive composition for medium / low nitrile NBR rubber adhesive according to an embodiment of the present invention is interposed between medium / low nitrile NBR rubber having a ACN content of 30 mol% or less, and the medium / low nitrile. A composition of an adhesive for bonding NBR rubber to the metal, the polymer comprising a phenol resin, NBR rubber and CPE (Chlorinated Polyethylene) rubber, and containing NBR / CPE rubber raw material having 30 to 70 parts by weight of the adhesive.
이 경우, 상기 NBR 고무는 상기 폴리머에서 55 내지 80 중량부를 가지며, CPE 고무는 상기 폴리머에서 20 중량부 대비 45 중량부를 가지는 것이 바람직하다. In this case, it is preferable that the NBR rubber has 55 to 80 parts by weight in the polymer, and the CPE rubber has 45 parts by weight relative to 20 parts by weight in the polymer.
또한, 본 발명은, 상기 폴리머 100 중량부 대비 0.2 내지 2 중량부를 가지며, 황(sulfur)으로 이루어진 가황제와, 상기 폴리머 100 중량부 대비 2 내지 8 중량부를 가지는 Tetramethyl Thiuram Disulfide와, 상기 폴리머 100 중량부 대비 2 내지 8 중량부를 가지는 N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide를 포함하는 가황 촉진제를 더 포함할 수 있다. In addition, the present invention, 0.2 to 2 parts by weight relative to 100 parts by weight of the polymer, sulfur vulcanizing agent (sulfur), Tetramethyl Thiuram Disulfide having 2 to 8 parts by weight relative to 100 parts by weight of the polymer, 100 parts by weight of the polymer It may further include a vulcanization accelerator including N-Cyclohexyl-2-benzothiazolesulfenamide having 2 to 8 parts by weight relative to N-Cyclohexyl-2-benzothiazolesulfenamide.
한편, 본 발명의 다른 측면에서, ACN 함량이 30%이하인 중/저니트릴 NBR 고무와 금속 사이에 개재되어서, 상기 중/저니트릴 NBR 고무를 상기 금속에 접착시키는 접착제를 제조하기 위한 용액으로서, 용제와, 상기 용액의 30 내지 70 중량부를 가지는 페놀 수지와, NBR 고무와, CPE고무를 폴리머로 하는 것으로, 상기 접착제의30 내지 70 중량부를 가지는 NBR/CPE 고무 원료를 포함하고, 상기 용제는, 상기 용액의 20 내지60 중량부를 가지는 메틸에틸케톤(methylethylketon)과, 상기 용액의 20 내지 60 중량부를 가지는 톨루엔(toluene)을 포함하는 것을 특징으로 하는 중/저 니트릴 NBR 고무 접착용 접착제 용액을 제공한다.On the other hand, in another aspect of the present invention, as a solution for preparing an adhesive for bonding the medium / low nitrile NBR rubber to the metal, interposed between the medium / low nitrile NBR rubber having an ACN content of 30% or less, And a phenol resin having 30 to 70 parts by weight of the solution, NBR rubber and CPE rubber as polymers, and containing NBR / CPE rubber raw materials having 30 to 70 parts by weight of the adhesive, wherein the solvent is Provided is an adhesive solution for medium / low nitrile NBR rubber adhesive, comprising methyl ethyl ketone having 20 to 60 parts by weight of a solution, and toluene having 20 to 60 parts by weight of the solution.
상기와 같은 구성을 가지는 본 발명에 의하면 중/저 니트릴 NBR 고무 접착용 접착제는, 수지계 접착제 대비 양호한 접착력을 가지는 동시에, 고무계 접착제 대비 내유성 및 내열성이 우수하게 된다, 따라서, 고무계 접착제에서 발생할 수 있는 접착제 탈락현상이 방지된다. According to the present invention having the above-described configuration, the adhesive for medium / low nitrile NBR rubber adhesive has a good adhesive strength compared to the resin adhesive, and also has excellent oil resistance and heat resistance compared to the rubber adhesive, and therefore, an adhesive that may occur in the rubber adhesive. Dropout is prevented.
이하, 본 발명의 바람직한 일 실시예를 상세하게 설명한다.Hereinafter, a preferred embodiment of the present invention will be described in detail.
본 발명의 바람직한 실시예에 따른 중/저 니트릴 NBR 고무 접착용 접착제 조성물은, 페놀 수지와, NBR/CPE 고무 원료를 포함한다.The adhesive composition for medium / low nitrile NBR rubber adhesion according to a preferred embodiment of the present invention includes a phenol resin and an NBR / CPE rubber raw material.
페놀 수지는 페놀류와 포름알데히드류의 축합에 의해서 생기는 열경화성(熱硬化性) 수지이다. 사용되는 페놀류는 석탄산이 주가 된다. 제조공정에서 사용되는 촉매에 따라 노볼락과 레졸을 각각 얻는데, 전자는 건식법으로 후자는 습식법으로 경화된다.Phenolic resin is a thermosetting resin produced by condensation of phenols and formaldehydes. The main phenols used are phenols. Depending on the catalyst used in the manufacturing process, novolak and resol are respectively obtained. The former is dried by the dry method and the latter is cured by the wet method.
상기 페놀 수지는 접착제의 내유성과 내열성을 향상시킨다. 이에 따라서 부족한 내열/내유성에 의해 접착제가 탈락되지 않아서, 접착제 피막이상대유의 흐름을 방해하지 않게 된다The phenolic resin improves oil resistance and heat resistance of the adhesive. Accordingly, the adhesive does not fall off due to insufficient heat / oil resistance, so that the flow of the abnormal film of the adhesive film is not disturbed.
NBR/CPE 고무 원료의 폴리머는 NBR 고무 및 CPE(Chlorinated Polyethylene) 고무로서 이루어진다. The polymer of NBR / CPE rubber raw material consists of NBR rubber and Chlorinated Polyethylene (CPE) rubber.
상기 NBR/CPE 고무 원료는 중/저니트릴 NBR 고무와의 접착력을 향상시킨다. 즉, 본 발명에 의하여 제조된 중/저 니트릴 NBR 고무 접착용 접착제가 NBR 고무를 접착시키는 것이므로, 상기 NBR 고무와 동일 소재를 베이스 폴리머로 사용하여서 접착력을 부가한다.The NBR / CPE rubber raw material improves adhesion with medium / low nitrile NBR rubber. That is, since the adhesive for adhesion of the medium / low nitrile NBR rubber prepared according to the present invention adheres the NBR rubber, an adhesive force is added using the same material as the NBR rubber as the base polymer.
본 발명의 NBR/CPE 고무 원료의 폴리머로 CPE 고무를 더 포함한다. The polymer of the NBR / CPE rubber raw material of the present invention further includes CPE rubber.
CPE 고무는 NBR 고무와 병용사용 시에는 내한성, 난연성, 내오존성, 내약품성과 분산성 등을 향상시키는특징이 있다. 또한, CPE 고무의 사용온도가 150℃로 내열성도 높다. 따라서 NBR 고무의 경우 내열성, 내오존성, 내약품성이 낮다는 불리함을, CPE 고무가 보완하는 효과가 있다.CPE rubber has features to improve cold resistance, flame retardancy, ozone resistance, chemical resistance and dispersibility when used in combination with NBR rubber. In addition, the CPE rubber has a high temperature resistance of 150 ° C. Therefore, in the case of NBR rubber, CPE rubber has the effect of compensating for the disadvantage of low heat resistance, ozone resistance and chemical resistance.
또한, CPE 고무는 기본적으로 CPE는 플라스틱과 고무 특성을 겸비하고 있다. 또한, 상기 CPE고무는 분자내 이중결합이 없어 내후성, 내오존성이 우수하며, 극성을 띠는 분자 특성으로 다른 수지와의 상용성이 뛰어나다. In addition, CPE rubber basically has the characteristics of plastic and rubber CPE. In addition, the CPE rubber is excellent in weather resistance and ozone resistance because there is no intramolecular double bond, and excellent polarity and compatibility with other resins.
상기 CPE고무는 페놀수지와 고무의 특성을 겸비하고 있으므로 두 제품의 혼합에 중간매체 역할을 한다. 따라서 NBR 고무와 페놀 수지간의 믹싱 효과를 최대한 좋도록 할 수 있다.즉, NBR 고무만으로는 페놀 수지와 컴파운딩하지 못하고, 내열성 및 내유성이 열화되므로, 본 발명에서는 NBR 고무에 CPE 고무를 혼합을 하여서 접착제를 제조함으로써, 중/저 니트릴 NBR고무에 대한 접착력과, 내열성 및 내유성을 동시에 향상시킬 수 있다. Since the CPE rubber combines the properties of phenolic resin and rubber, it acts as an intermediate in the mixing of the two products. Therefore, the mixing effect between NBR rubber and phenolic resin can be maximized. That is, since NBR rubber alone does not compound with phenolic resin, and heat resistance and oil resistance deteriorate, in the present invention, adhesives are obtained by mixing CPE rubber with NBR rubber. By manufacturing the above, it is possible to improve the adhesion to the medium / low nitrile NBR rubber, heat resistance and oil resistance at the same time.
본 발명에 의하면, 상기 고무의 내열성 및 내유성 저하는 페놀 수지에 의하여 해결된다. 또한 페놀 수지의 접착성 저하는 NBR/CPE 고무 원료로서 해결된다. According to this invention, the heat resistance and oil resistance fall of the said rubber | gum are solved by a phenol resin. In addition, the adhesive lowering of the phenol resin is solved as an NBR / CPE rubber raw material.
이 경우, 페놀수지는 상기 접착제의 30 내지 70 중량부를 가지는 것이 바람직하다. 또한, NBR/CPE 고무 원료 또한 상기 접착제의 30 내지 70 중량부를 가지는 것이 바람직하다.In this case, the phenol resin preferably has 30 to 70 parts by weight of the adhesive. In addition, the NBR / CPE rubber raw material also preferably has 30 to 70 parts by weight of the adhesive.
한편, NBR 고무는 상기 폴리머에서 55 내지 80 중량부를 가지며, CPE 고무는 상기 폴리머에서 20 중량부 대비 45중량부를 가지는 것이 바람직하다. 이는 상기 NBR 고무가 상기 폴리머에서 80 중량부를 초과하는 경우에는 내유성/ 내열성이 열화되고, 상기 페놀 수지와의 결합성이 떨어지고, 55 중량부보다 낮은 경우에는 접착성이 떨어지기 때문이다. On the other hand, NBR rubber is preferably 55 to 80 parts by weight in the polymer, CPE rubber is preferably 45 parts by weight relative to 20 parts by weight in the polymer. This is because when the NBR rubber exceeds 80 parts by weight of the polymer, oil resistance / heat resistance deteriorates, the bond with the phenol resin is inferior, and when the NBR rubber is lower than 55 parts by weight, the adhesion is inferior.
한편, 상기 NBR/CPE 고무 원료는 가황제 및 가황촉진제를 더 포함할 수 있다. On the other hand, the NBR / CPE rubber raw material may further include a vulcanizing agent and a vulcanization accelerator.
가황제는 상기 폴리머를 구성하는 단량체들을 상호 가교하는 기능을 한다. 상기 가교제는 황(sufur)을 포함할 수 있다. 이 경우, 상기 가황제는, 상기 폴리머 100 중량부에 대하여 0.2 내지 2 중량부를 가질 수 있다.The vulcanizing agent functions to crosslink the monomers constituting the polymer. The crosslinking agent may comprise sufur. In this case, the vulcanizing agent may have 0.2 to 2 parts by weight based on 100 parts by weight of the polymer.
가황 촉진제는 황시간의 단축, 가황온도의 저하, 가황제의 양을 감소시켜 고무제품의 품질향상을 목적으로 사용된다. 본 발명에서는, 가황 촉진제로, 상기 폴리머 100 중량부 대비 2 내지 8 중량부를가지는 Tetramethyl Thiuram Disulfide와, 상기 폴리머 100 중량부 대비 2 내지 8 중량부를 가지는 N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide를 포함할 수 있다.Vulcanization accelerators are used for the purpose of improving the quality of rubber products by shortening the sulfur time, lowering the vulcanization temperature and reducing the amount of vulcanizing agent. In the present invention, a vulcanization accelerator, Tetramethyl Thiuram Disulfide having 2 to 8 parts by weight based on 100 parts by weight of the polymer, and N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide having 2 to 8 parts by weight based on 100 parts by weight of the polymer. It may include.
한편, 상기 페놀 수지와, NBR/CPE 고무 원료를 컴파운딩하기 위하여 용제가 필요하다. 상기 용제는 용해성 및 휘발성이 우수한 소재로 이루어지는 것이 바람직하며, 이 경우, 메틸에틸케톤(methylethylketon)과, 톨루엔(toluene)을 포함할 수 있다. 상기 용제는 용기에 담겨 있으며, 상기 페놀 수지와, NBR/CPE 고무 원료가 상기 용제 용기에 투입되어서 믹싱 및 컴파운딩됨으로써 중/저 니트릴 NBR 고무 접착용 접착제 용액이 이루어질 수 있다. On the other hand, a solvent is required to compound the phenol resin and the NBR / CPE rubber raw material. The solvent is preferably made of a material having excellent solubility and volatility. In this case, the solvent may include methyl ethyl ketone and toluene. The solvent is contained in a container, and the phenolic resin and the NBR / CPE rubber raw material are added to the solvent container, and mixed and compounded to form a medium / low nitrile NBR rubber adhesive adhesive solution.
이 경우, 페놀 수지는 상기 접착제 용액의 1 내지 10 중량부를 가지고, 상기 NBR 고무는 상기 접착제 용액의 1 내지 10 중량부를 가지고, CPE고무는 상기 접착제 용액의 1 내지 10 중량부를 가지고, 메틸에틸케톤은 상기 용액의 20 내지 60 중량부를 가지고, 톨루엔은 접착제 용액의 1 내지 10 중량부를 가지는 것이 바람직하다.In this case, the phenol resin has 1 to 10 parts by weight of the adhesive solution, the NBR rubber has 1 to 10 parts by weight of the adhesive solution, CPE rubber has 1 to 10 parts by weight of the adhesive solution, and methyl ethyl ketone is It is preferable to have 20 to 60 parts by weight of the solution, and toluene has 1 to 10 parts by weight of the adhesive solution.
상기 접착제를 이용하여, 중/저니트릴 NBR 고무를 금속에 결합시키는 공정을 간단히 설명하면, 금속 표면에 접착제 부착이 용이하도록, 상기 금속 표면에 묻어 있는 오일이나 이물을 제거하고 숏트나 인산염결정을 생성시키는 등의 전처리를 한다. 그 후에 금속을 접착제 용액에 침적시킨 후 꺼낸다. Using the adhesive, the process of bonding the medium / low nitrile NBR rubber to the metal is briefly described. To facilitate adhesion of the adhesive to the metal surface, the oil or foreign matter on the metal surface is removed to form a short or phosphate crystal. Pretreatment such as The metal is then immersed in the adhesive solution and then taken out.
그 후에 금속에 묻어 있는 접착제 용액 중 접착제 성분만 남기고 용제는 제거하고 금속에 접착제를 고착시키기 위해서 130~200도 사이의 온도로 가열한다. 이 가열시간 동안 접착제가 경화된다. 그 후 가열된 금형 안에 NBR 고무와 접착제가 도포된 제품철을 넣고 압력을 가하면 접착제와 고무가 반응을 일으켜 접착이 되게 된다After that, the solvent is removed from the adhesive solution on the metal and the solvent is removed and heated to a temperature between 130 and 200 degrees to fix the adhesive on the metal. The adhesive cures during this heating time. After that, put NBR rubber and adhesive coated product iron in the heated mold and apply pressure to make the adhesive react with the rubber.
이하에서는, 상기와 같은 본 발명의 실시예에 따른 중/저 니트릴 NBR 고무 접착용 접착제 조성물(이하 편의상 실시예라고 칭함.)을 종래의 페놀 수지로 이루어진 접착제 조성물(이하, 편의상 비교예라고 칭함.)간의 성질을 각종 테스트하여 서로 비교함으로써, 상기 효과를 더욱 명확하게 설명한다.Hereinafter, the adhesive composition for the low / low nitrile NBR rubber adhesive according to the embodiment of the present invention as described above (hereinafter referred to as Example) is made of a conventional phenol resin adhesive composition (hereinafter referred to as comparative example for convenience). The above effects are more clearly explained by comparing the properties between the two tests and comparing them with each other.
표 1은 상기 각종 테스트에 적용되는 실시예와 비교예의 구성성분을 비교하여 나타낸 표이다. Table 1 is a table comparing the components of the Examples and Comparative Examples applied to the various tests.
2) CPE : Chlorinated Polyethylene Rubber(합성고무), CPE 6135, Weifang Yaxing Chemical
3) TD-870 : Novolac Resin + Hexamethylenetetramine, 강남화성
4) MIDAS 101 : Sulfur, 미원상사
5) Vulkacit Thiuram/C : Tetramethyl Thiuram Disulfide, Lanxess
6) Vulkacit CZ/EG/C : N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide, Lanxess1) NBR: Nitrile Butadiene Rubber (synthetic rubber), B6280, LG Chemical
2) CPE: Chlorinated Polyethylene Rubber (Synthetic Rubber), CPE 6135, Weifang Yaxing Chemical
3) TD-870: Novolac Resin + Hexamethylenetetramine, Gangnam Hwaseong
4) MIDAS 101: Sulfur, Miwon Corporation
5) Vulkacit Thiuram / C: Tetramethyl Thiuram Disulfide, Lanxess
6) Vulkacit CZ / EG / C: N-Cyclohexyl-2-benzothiazolesulfenamide N-Cyclohexyl-2-benzothiazolesulfenamide, Lanxess
표 2는 고무 잔유율 시험 결과를 나타난 표이다. 이 경우, 고무 잔유율은 고무와 접착된 금속 시편에서 고무를 강제 박리시켰을 때, 금속 표면에서 탈락되지 않고 남아있는 고무의 면적을 전체 면적으로 나눈 값을 나타낸다.Table 2 is a table showing the rubber residual test results. In this case, the rubber residual ratio represents a value obtained by dividing the area of the rubber remaining without dropping from the metal surface by the total area when the rubber is forcibly peeled off from the metal specimen bonded to the rubber.
시험조건은 KS M 6787 "가황고무의 접착시험방법"에 기재되어 있는 "금속편과 고무의 90도 박리시험"에 따라 물림구의 이동속도를 50ㅁ5.0mm로 하여 시험하였다.The test conditions were tested according to the "90 degree peeling test of metal pieces and rubber" described in KS M 6787 "Adhesion Testing Method of Vulcanized Rubber" with a moving speed of 50 5.0 5.0 mm.
이에 사용된 금속 시편에 접착된 고무는 ACN이 21%에서 34%인 NBR 고무로서, 상기 가교제로서는 상기 폴리머 100 중량부에 대하여 3 중량부를 갖는 트리알릴이소시아누레이트(triallkyisocyanurate)하고, 가교제는, 상기 폴리머 100 중량부에 대하여 7 중량부를 갖는 유기과산화물이고, 충진제는 카본 블랙 및 실리콘디옥사이드(SiO2)을 포함하고, 상기 가공조제는 파라핀 마이크로 왁스를 포함하며, 상기 가소제는 디에스테르(diester)계를 사용하였다. 또한 노화방지제는 N-Phenyl-N'-Isopropyl-P-Phenylendiamine과, 2,4-Trimethyl-1,2-dihydroquinoline와, 2-Mercaptobenzimidiazole로 이루어졌다.The rubber adhered to the metal specimen used therein is NBR rubber having an ACN of 21% to 34%, and as the crosslinking agent, triallyl isocyanurate having 3 parts by weight with respect to 100 parts by weight of the polymer, the crosslinking agent, The organic peroxide having 7 parts by weight based on 100 parts by weight of the polymer, the filler comprises carbon black and silicon dioxide (SiO2), the processing aid comprises a paraffin microwax, the plasticizer comprises a diester system (diester) Used. In addition, anti-aging agent was composed of N-Phenyl-N'-Isopropyl-P-Phenylendiamine, 2,4-Trimethyl-1,2-dihydroquinoline, and 2-Mercaptobenzimidiazole.
이 경우, ACN 값은 단일 NBR 고무를 사용하여서 맞추기도 하였고, 두 종류의 다른 ACN 값을 갖는 NBR 고무를 블랜딩하여서 맞추기도 하였다. In this case, the ACN values were adjusted using a single NBR rubber, or by blending NBR rubbers with two different ACN values.
표 2에서 #1 및#2에 기재된 N250S, NT1846F 등은 ㈜평화오일씰에서 제조되어 판매되는 상품으로서 각각의 ACN 함량을 가지고 있다. N250S, NT1846F, and the like described in Tables # 1 and # 2 in Table 2 are manufactured and sold by Pyung Hwa Oil Seal Co., Ltd. and have respective ACN contents.
또한, 접착시편은 KS M 6787 "가황고무의 접착시험방법"에 기재되어 있는 시험편의 모양 및 치수에 따라 두께 6.0ㅁ0.1mm, 나비 25.0ㅁ0.1mm, 길이 125mm의 고무를 두께 1.5ㅁ0.1mm, 나비 25.0ㅁ0.1mm, 길이 60ㅁ1mm, 냉간압연강판 재질의 금속시편에 접착시켜 사용하였다.In addition, the adhesive specimens may be made of rubber having a thickness of 6.0 W 0.1 mm, butterfly 25.0 W 0.1 mm and a length of 125 mm according to the shape and dimensions of the test pieces described in KS M 6787 "Adhesion Test Method of Vulcanized Rubber". A butterfly 25.0 ㅁ 0.1 mm, length 60 ㅁ 1 mm, was used by bonding to a metal specimen made of cold rolled steel sheet.
그 결과 표 2에 기재된 바와 같이, 실시예의 경우 ACN 함량에 관계없이 접착된 고무의 잔유률이 99% 이상인 것을 알 수 있다. As a result, as shown in Table 2, in the case of the embodiment it can be seen that the residual ratio of the bonded rubber is 99% or more regardless of the ACN content.
이와 달리 비교예의 경우, ACN함량이 30% 이상인 중니트릴 NBR인 경우에는 접착된 고무의 잔유률이 99% 이상으로 나타나나, ACN 함량이 30% 미만인 중/저 니트릴 NBR 고무의 경우에는 고무 잔유율이 현저하게 낮아짐을 알 수 있고, 대부분의 경우는 5% 미만인 것을 알 수 있다. In contrast, in the comparative example, in the case of the medium nitrile NBR having an ACN content of 30% or more, the residual ratio of the bonded rubber was 99% or more, but in the case of the medium / low nitrile NBR rubber having an ACN content of less than 30%, the rubber residual rate was It can be seen that this is significantly lower, in most cases it is less than 5%.
따라서 본 발명의 경우, 종래의 페놀 수지로 이루어진 접착제 대비하여서, ACN 함량이 30mol% 이하인 경우 접착율이 월등하게 우수하다는 것을 알 수 있다.
Therefore, in the case of the present invention, it can be seen that the adhesion rate is excellent when the ACN content is less than 30mol% compared to the adhesive made of a conventional phenol resin.
상술한 바와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만 해당 기술분야의 숙련된 당업자라면 하기의 청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, although described with reference to the preferred embodiment of the present invention, those skilled in the art various modifications and variations of the present invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.
Claims (4)
페놀 수지; 및
NBR 고무와, CPE(Chlorinated Polyethylene)고무를 폴리머로 하며, 상기 접착제의 30 내지 70 중량부를 가지는 NBR/CPE 고무 원료;
를 포함하는 것을 특징으로 하는 중/저 니트릴 NBR 고무 접착용 접착제 조성물. As a composition of an adhesive which is interposed between a medium / low nitrile NBR rubber having an ACN content of 30 mol% or less and a metal, thereby adhering the medium / low nitrile NBR rubber to the metal,
Phenolic resins; And
NBR rubber and CPE (Chlorinated Polyethylene) rubber as a polymer, NBR / CPE rubber raw material having 30 to 70 parts by weight of the adhesive;
Medium / low nitrile NBR rubber adhesive composition comprising a.
상기 NBR 고무는 상기 폴리머에서 55 내지 80 중량부를 가지며, CPE 고무는 상기 폴리머에서 20 중량부 대비 45 중량부를 가지는 것을 특징으로 하는 중/저 니트릴 NBR 고무 접착용 접착제 조성물.The method of claim 1,
The NBR rubber has 55 to 80 parts by weight in the polymer, CPE rubber has a weight of 45 parts by weight relative to 20 parts by weight in the polymer adhesive composition for adhesive NBR rubber.
상기 폴리머 100 중량부 대비 0.2 내지 2 중량부를 가지며, 황(sulfur)으로 이루어진 가황제; 및
상기 폴리머 100 중량부 대비 2 내지 8 중량부를 가지는 Tetramethyl Thiuram Disulfide와, 상기 폴리머 100 중량부 대비 2 내지 8 중량부를 가지는 N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide를 포함하는 가황 촉진제;
를 더 포함하는 것을 특징으로 하는 중/저 니트릴 NBR 고무 접착용 접착제 조성물.The method of claim 1,
A vulcanizing agent having 0.2 to 2 parts by weight relative to 100 parts by weight of the polymer and composed of sulfur; And
Vulcanization accelerator comprising Tetramethyl Thiuram Disulfide having 2 to 8 parts by weight based on 100 parts by weight of the polymer, and N-Cyclohexyl-2-benzothiazolesulfenamideN-Cyclohexyl-2-benzothiazolesulfenamide having 2 to 8 parts by weight with respect to 100 parts by weight of the polymer;
Medium / low nitrile NBR rubber adhesive adhesive composition comprising a further.
용제;
상기 용액의 30 내지 70 중량부를 가지는 페놀 수지; 및
NBR 고무와, CPE고무를 폴리머로 하는 것으로, 상기 접착제의30 내지 70 중량부를 가지는 NBR/CPE 고무 원료를 포함하고,
상기 용제는, 상기 용액의 20 내지 60 중량부를 가지는 메틸에틸케톤(methylethylketon)과, 상기 용액의 20 내지 60 중량부를 가지는 톨루엔(toluene)을 포함하는 것을 특징으로 하는 중/저 니트릴 NBR 고무 접착용 접착제 용액.As a solution for producing an adhesive interposed between a medium / low nitrile NBR rubber having an ACN content of 30 mol% or less and a metal, thereby adhering the medium / low nitrile NBR rubber to the metal,
solvent;
Phenolic resin having 30 to 70 parts by weight of the solution; And
NBR rubber and CPE rubber as a polymer, including NBR / CPE rubber raw material having 30 to 70 parts by weight of the adhesive,
The solvent comprises methyl ethyl ketone having 20 to 60 parts by weight of the solution, and toluene having 20 to 60 parts by weight of the solution. solution.
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| KR1020110099247A KR20130035033A (en) | 2011-09-29 | 2011-09-29 | Adhesives composite for adhereing low-acn nbr and adhesives solution for adhereing low-acn nbr |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200137407A (en) * | 2019-05-30 | 2020-12-09 | 피씨케이(주) | High performance rubber adhesive composition using modified graphene |
| KR20210116124A (en) * | 2020-03-17 | 2021-09-27 | 평화오일씰공업주식회사 | Coating material and Coupling in coolant line including the coating material |
| KR20210118533A (en) * | 2020-03-23 | 2021-10-01 | 이동원 | Adhesive composition for bonding rubber and metal |
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2011
- 2011-09-29 KR KR1020110099247A patent/KR20130035033A/en not_active Ceased
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200137407A (en) * | 2019-05-30 | 2020-12-09 | 피씨케이(주) | High performance rubber adhesive composition using modified graphene |
| KR20210116124A (en) * | 2020-03-17 | 2021-09-27 | 평화오일씰공업주식회사 | Coating material and Coupling in coolant line including the coating material |
| KR20210118533A (en) * | 2020-03-23 | 2021-10-01 | 이동원 | Adhesive composition for bonding rubber and metal |
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