JPH02103247A - Ethylene-propylene rubber composition - Google Patents
Ethylene-propylene rubber compositionInfo
- Publication number
- JPH02103247A JPH02103247A JP25766988A JP25766988A JPH02103247A JP H02103247 A JPH02103247 A JP H02103247A JP 25766988 A JP25766988 A JP 25766988A JP 25766988 A JP25766988 A JP 25766988A JP H02103247 A JPH02103247 A JP H02103247A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- parts
- ethylene
- vulcanized
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229920000181 Ethylene propylene rubber Polymers 0.000 title abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 63
- 239000005060 rubber Substances 0.000 claims abstract description 63
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 2
- 239000004636 vulcanized rubber Substances 0.000 abstract description 26
- 238000004073 vulcanization Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- -1 ethylene, propylene Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001007 puffing effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- 229910016455 AlBN Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は加硫接着性が改良されたエチレン・プロピレン
系ゴム組成物に関するものである。さらに詳しくは、自
動車用部品や工業用途に使用されるエチレン・プロピレ
ン共重合ゴム（以下ＥＰＲと略称する）又はエチレン・
プロピレン・非共役ジエン三元共重合ゴム（以下ＥＰＤ
Ｍと略称する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an ethylene-propylene rubber composition with improved vulcanization adhesion. More specifically, ethylene/propylene copolymer rubber (hereinafter abbreviated as EPR) or ethylene/propylene copolymer rubber used for automobile parts and industrial purposes is
Propylene/non-conjugated diene terpolymer rubber (EPD)
It is abbreviated as M.
またＥＰＲとＥＰＤＭとを総称してエチレン・プロピレ
ン系ゴムと言い、これをＥＰ系ゴムと略称する）に疎水
性マクロモノマーを含有する、耐水■湿接着性の改良の
改良されたＥＰ系ゴム組成杓に関するものである。In addition, EPR and EPDM are collectively referred to as ethylene-propylene rubber, and this is abbreviated as EP rubber), which contains a hydrophobic macromonomer, and is an improved EP rubber composition with improved water resistance and wet adhesion. It's about the ladle.
従来の技術
従来ＥＰ系ゴムの接着は、未加硫ゴム同士は容易に接着
することができが、加硫ゴムと未加硫ゴムとの接着や、
加硫ゴム同士の接着は、極めて困難である。Conventional technology When adhering conventional EP rubber, unvulcanized rubbers can be easily adhered to each other, but adhesion between vulcanized rubber and unvulcanized rubber,
Adhesion between vulcanized rubbers is extremely difficult.
一／１２にＥＰ系ゴムの加硫ゴムと未加硫ゴムとを接着
する方法としては、加硫ゴムの表面をパフ処理し、その
処理面に未加硫ゴムを重ねて加硫接着する方法や、ＢＰ
系ゴム組成物中にアルキルフェノール樹脂を含有させて
加硫接着する方法等が知られている。1/12 A method for bonding vulcanized EP rubber and unvulcanized rubber is to puff the surface of the vulcanized rubber, overlap the unvulcanized rubber on the treated surface, and vulcanize and bond. Ya, BP
A method of vulcanization bonding by incorporating an alkylphenol resin into a rubber composition is known.
また加硫ゴム同士を接着する手段としては、その加硫ゴ
ムの間に未加硫ゴムを挾んで加硫接着することが行われ
ている。この場合、前述の加硫ゴムと未加硫ゴムとの接
着の場合と同様に、パフ処理やアルキルフェノール樹脂
の配合等の手段が使用される。またシアノアクリレート
、イソシアネート、クロロブレン系等の接着剤を用いて
接着することも行われている。Moreover, as a means for bonding vulcanized rubbers together, unvulcanized rubber is sandwiched between the vulcanized rubbers and vulcanized and bonded. In this case, as in the case of adhesion between vulcanized rubber and unvulcanized rubber described above, means such as puffing and blending of an alkylphenol resin are used. Additionally, bonding is also carried out using cyanoacrylate, isocyanate, chloroprene adhesives, and the like.
発明が解決しようとする問題点
しかしながら前記従来の方法は、それぞれ問題点を有し
ている。加硫ゴムの表面をパフ処理するのは作業性に劣
り、またアルキルフェノール樹脂を含有する方法では、
湿度か高い場合に耐水・耐；易接着性が劣る。さらに接
着剤により接着する方法では、シアノアクリレート系接
着剤は接着力は良好であるものの接着部が硬くなり、ク
ロロプレン系接着剤は接着力が弱い。Problems to be Solved by the Invention However, each of the above-mentioned conventional methods has its own problems. Puffing the surface of vulcanized rubber has poor workability, and methods involving alkylphenol resins
Water resistance and resistance when humidity is high; adhesive properties are poor. Furthermore, in the method of bonding with adhesives, cyanoacrylate adhesives have good adhesive strength but the bonded portion becomes hard, and chloroprene adhesives have weak adhesive strength.
本発明はかかる事情に鑑みなされたものであって、加硫
ゴムに対して未加硫ゴムを接着するに際し、加硫接着性
に侵れ、高水準の初期接着力を示すと共に、長期に互っ
て耐水・耐湿接着性を有するゴム組成物を提供すること
を目的とするもので、ある。The present invention has been developed in view of the above circumstances, and is designed to prevent the vulcanization adhesion from eroding when bonding unvulcanized rubber to vulcanized rubber, exhibit high initial adhesive strength, and maintain long-term compatibility. The purpose of this invention is to provide a rubber composition having water-resistant and moisture-resistant adhesive properties.
問題へを解決する手段
而して本発明は、エチレン・プロピレン系ゴム１００重
量部に対し、疎水性マクロモノマーを０゜１を皿部以上
５０重量部未満含有することを特徴とするものである。As a means to solve the problem, the present invention is characterized in that the hydrophobic macromonomer is contained in a dish portion or more and less than 50 parts by weight of a hydrophobic macromonomer based on 100 parts by weight of ethylene-propylene rubber. .
本発明におけるＥＰ系ゴムは、ＥＰＲ及び、ＥＰＤＭを
含む、ＥＰＲは、エチレンとプロピレンとよりなるゴム
状共重合体であり、まなＥＰＤＭは、エチレンと、プロ
ピレンと、ジシクロペンタジェン、エチリデンノルボル
ネン、１，４−へキサジエン、メチルノルボルネン、４
，７，８．９テトラヒドロインデン等の非共没ジエンと
の、王者を共重合させてなる、低不飽和ゴム状共重合体
である。The EP rubber in the present invention includes EPR and EPDM. EPR is a rubbery copolymer made of ethylene and propylene, and EPDM is a rubbery copolymer made of ethylene, propylene, dicyclopentadiene, ethylidenenorbornene, 1,4-hexadiene, methylnorbornene, 4
, 7, 8.9 It is a low unsaturated rubbery copolymer obtained by copolymerizing the king with a non-encomprehended diene such as tetrahydroindene.
これらのＥＰ系ゴムは、それ単独で使用することもでき
るが、これを主体として、他の天然ゴム又は、５ＢＲ１
ＩＲ，ＢＲ等の合成ゴムとブレンドして使用することら
可能である。These EP rubbers can be used alone, but they can also be used as a main component with other natural rubbers or 5BR1.
It is possible to use it by blending it with synthetic rubbers such as IR and BR.
次に、本発明において使用される疎水性マクロモノマー
とは、分子鎖の片末端又は両末端に、重縮合し得る官能
基を有する比教的高分子Ｘ（数平均分子量で１０００〜
２００００）の、疎水性モノマーを言う。Next, the hydrophobic macromonomer used in the present invention refers to a religious polymer X (number average molecular weight of 1,000 to 1,000
20,000) is a hydrophobic monomer.
この疎水性マクロモノマーの骨格構造としては、ビニル
重合性モノマーの重合体骨格が適当である６その具体例
としては、酢酸ビニル、スチレン、スチレン誘導体、メ
タクリル酸メチル、アクリル酸エステル、メタアクリロ
ニトリル、Ｎ−ビニル化合物等のモノマーの重合体が挙
げられる。またこれらの重合体は、モノマーを単独で重
合したものであってもよく、二種以上のものを共重合し
たものであってもよい。As the skeleton structure of this hydrophobic macromonomer, a polymer skeleton of a vinyl polymerizable monomer is suitable.6 Specific examples thereof include vinyl acetate, styrene, styrene derivatives, methyl methacrylate, acrylic acid ester, methacrylonitrile, N - Polymers of monomers such as vinyl compounds. Moreover, these polymers may be those obtained by polymerizing a single monomer, or may be those obtained by copolymerizing two or more types of monomers.
また当該疎水性マクロモノマーの末端官能基としては、
アクリロイルオキシ基、メタクリロイル基、アクリロイ
ル基、スチリル基等のビニル重合性基又は、ジカルボキ
シル基、カルボキシル基、ジヒドロキジル基、ヒドロカ
シル基等が適用される。In addition, the terminal functional group of the hydrophobic macromonomer is as follows:
Vinyl polymerizable groups such as acryloyloxy, methacryloyl, acryloyl, and styryl groups, dicarboxyl, carboxyl, dihydroxyl, and hydrocasyl groups are applicable.
この疎水性マクロモノマーを製造する方法としては、導
入したい末端官能基に対応する連鎖移動剤の存在下で、
骨格を構成すべきラジカル重合性モノマーを重合させて
、片末端に前記官能基を有する疎水性マクロモノマーを
得る方法を挙げることができる。The method for producing this hydrophobic macromonomer is as follows: in the presence of a chain transfer agent corresponding to the terminal functional group to be introduced.
A method for obtaining a hydrophobic macromonomer having the above-mentioned functional group at one end by polymerizing a radically polymerizable monomer to constitute a skeleton can be mentioned.
重合の方法としては、従来公知のラジカル重合開始剤の
存在の下に、溶液重合法、バルク重合法、エマルジョン
重合法、！賢濁重合法等の方法で反応させればよいが、
反応の簡便さ等から、）容液重合法が好適である。Polymerization methods include solution polymerization, bulk polymerization, emulsion polymerization, etc. in the presence of conventionally known radical polymerization initiators. The reaction may be carried out using a method such as a cloudy polymerization method, but
In view of the simplicity of the reaction, etc., the liquid polymerization method is preferred.
本発明で使用される疎水性マクロモノマーの量は、ＥＰ
系ゴム１００重量部に対して、０．１重量部以上５０重
量部未満とするのか適当である。The amount of hydrophobic macromonomer used in the present invention is
It is appropriate to set the amount to 0.1 parts by weight or more and less than 50 parts by weight based on 100 parts by weight of the rubber.
さらに好ましくは、３重量部以上２０重量部未満とする
のが良い。３重量部未満では本発明の効果が乏しく、ま
た２０重量部以上添加しても、それに見合う顕著な効果
が見られない。しかしながら０．１重量部以上添加して
いれば、乏しいながらも一応の効果が見られる。また５
０重量部未満の量は添加可能であるが、それ以上添加す
ると、ＥＰ系ゴムとしての物性に悪影響を及ぼす可能性
があり、好ましくない。More preferably, the amount is 3 parts by weight or more and less than 20 parts by weight. If it is less than 3 parts by weight, the effect of the present invention will be poor, and even if it is added in excess of 20 parts by weight, no correspondingly significant effect will be seen. However, if 0.1 part by weight or more is added, some effect can be seen, although it is poor. Also 5
Although it can be added in an amount of less than 0 parts by weight, adding more than that may have an adverse effect on the physical properties of the EP rubber, which is not preferable.
本発明のＥＰ系ゴム組成物は、必要に応じて通常用いら
れるゴムの加硫用配合剤、無１１（充填剤、軟化剤、そ
の曲の配合剤を、適宜配合することができる。The EP rubber composition of the present invention may optionally contain commonly used rubber vulcanization compounding agents, fillers, softeners, and other compounding agents.
配合剤の例としては、パーオキサイド類、硫黄、フェノ
ール樹脂、金属酸化物等の加硫剤、テトラメチルチウラ
Ｊ２ジスルフィド、ジペンタンメチレンチウラムテトラ
スルフィド等のチウラム系加硫促進剤、２−メルカプト
ベンゾチアゾール等のチアゾール系加硫促進剤、カーボ
ンブラック、含水硅酸、炭酸カルシウム、クレー等の無
機充填剤、プロセスオイル等の軟化剤などを挙げること
かできる。Examples of compounding agents include peroxides, sulfur, phenolic resins, vulcanizing agents such as metal oxides, thiuram vulcanization accelerators such as tetramethylthiura J2 disulfide, dipentane methylenethiuram tetrasulfide, and 2-mercaptobenzo. Examples include thiazole-based vulcanization accelerators such as thiazole, inorganic fillers such as carbon black, hydrated silicic acid, calcium carbonate, and clay, and softeners such as process oil.
本発明のＥＰ系ゴム組成物は、ＥＰ系ゴムと配合剤との
混練物中に、疎水性マクロモノマーを添加することによ
り、未加硫ゴム組成物を得る。ＥＰ系ゴムに疎水性マク
ロモノマーを添加する方法としては、オープンロール、
ボールミル、バンバＪ−ミキサー、ニーダ−等を用いて
、公知の方法で配合することができる。The EP rubber composition of the present invention is obtained by adding a hydrophobic macromonomer to a kneaded mixture of EP rubber and a compounding agent to obtain an unvulcanized rubber composition. Methods for adding hydrophobic macromonomers to EP rubber include open roll,
They can be blended by a known method using a ball mill, Bamba J-mixer, kneader, or the like.
また、ＥＰ系ゴムに疎水性マクロモノマーを含有せしめ
る池の方法として、ＥＰ系ゴムを溶液重合するに際し、
疎水性モノマーを非共役ジエンにグラフト重合させて導
入することもできる９本発明のＥＰ系ゴム組成物は、こ
れを未加硫ゴムとして１吏用し、他の加硫ゴムに対して
加硫接着することもでき、また加硫ゴムとして１重用し
、これに未加硫ゴムを加硫接着することもできる。すな
わぢ未加硫ゴムと加硫ゴムとを加硫接着するに際し、本
発明をその未加硫ゴムとしても加硫ゴムとしても使用す
ることができ、その両者に本発明を１吏川することもて
′きる。In addition, as a method for incorporating hydrophobic macromonomers into EP rubber, when solution polymerizing EP rubber,
A hydrophobic monomer can also be introduced by graft polymerization to a non-conjugated diene.9 The EP-based rubber composition of the present invention is used once as an unvulcanized rubber, and then vulcanized with another vulcanized rubber. It can be bonded, or it can be used as a single layer of vulcanized rubber and unvulcanized rubber can be vulcanized and bonded thereto. In other words, when vulcanizing and adhering unvulcanized rubber and vulcanized rubber, the present invention can be used as both the unvulcanized rubber and the vulcanized rubber, and the present invention applies to both. I can't stand it.
未加硫ゴムと加硫ゴｌ＼とのいずれかに本発明を使用し
ない場合には、従来公知の適宜の組成物を１史用すれば
よい。If the present invention is not used for either unvulcanized rubber or vulcanized rubber, any conventionally known appropriate composition may be used.
実施例 以下本発明の詳細な説明する。Example The present invention will be explained in detail below.
疎水性マクロモノマーの製造
マク１７モノマー１ メタクリル酸メチルマクロモノマ
ー
メタクリル酸メチル（以下ＭＭＡと略す）１５０重量部
、メチルイソブチルケトン３００重量部、アゾビスイソ
ブチロニトリル（以下ＡＩＢＮと略す）０８重量部、３
−メルカプトプロピオン酸１．０６重量部をカラスフラ
スコに仕込み、窒素置換して（ｒｌ、？品を８０°Ｃに
まて゛カロ１品昇ン品した。そして液温を８０°Ｃに維
持しながら、ＭＭＡ３５０重量部、ＡｌＢＮ２．０重量
部、３−メルカプトプロピオン酸４．５重量部の混合液
を、２時間かけて連続滴下しな。Production of hydrophobic macromonomer Mac 17 Monomer 1 Methyl methacrylate macromonomer Methyl methacrylate (hereinafter abbreviated as MMA) 150 parts by weight, methyl isobutyl ketone 300 parts by weight, azobisisobutyronitrile (hereinafter abbreviated as AIBN) 08 parts by weight ,3
- 1.06 parts by weight of mercaptopropionic acid was charged into a glass flask, and the atmosphere was replaced with nitrogen (rl, ?). A mixed solution of 350 parts by weight of MMA, 2.0 parts by weight of AlBN, and 4.5 parts by weight of 3-mercaptopropionic acid was continuously added dropwise over 2 hours.
滴下後さらに同温度で４時間反応させた後、メタクリル
酸りリシジル９．２５重量部、パイトロキノンモノメチ
ルエーテル０．１７重量部及び、テ１〜ラブチルアンモ
ニウムブロマイド４．２５重量部を添加し、加熱昇温し
て９０°Ｃで８時間反応させた。After the dropwise addition, the mixture was further reacted at the same temperature for 4 hours, and then 9.25 parts by weight of lysidyl methacrylate, 0.17 parts by weight of pytroquinone monomethyl ether, and 4.25 parts by weight of Te1-butylammonium bromide were added. The temperature was raised and the mixture was reacted at 90°C for 8 hours.
得られた反応液１００重量部をメタノール１００重量部
中に徐々に投入して、ＭＭＡマクロモノマーを析出さぜ
、その析出物と溶液とを分離しな。100 parts by weight of the obtained reaction solution was gradually poured into 100 parts by weight of methanol to precipitate the MMA macromonomer, and the precipitate was separated from the solution.
分離したＭ Ｍ Ａマクロモノマーを８５°Ｃで真空乾
燥して、精製された固形ＩＶＩ Ｍ Ａマクロモノマー
を得た。The separated M M A macromonomer was vacuum dried at 85°C to obtain a purified solid IVI M A macromonomer.
マクロモノマー２ 末端ジカルボン酸型ＭＭＡマクロモ
ノマー
ＭＭＡ１００重、置部、チオリンゴ酸３重量部、ＡｌＢ
Ｎ６．６重量部、メチルエチルケトン１００重量部を仕
込み、窒素置換して液温を７５°Ｃに力１１熱昇ｉ品し
た。そしてン５ｉ品を７５°Ｃに維持しつつ、〜ＩＭＡ
１００重量部、チオリンゴ酸９重量部、ＡｌＢＮ６．６
重量部、メチルエチルゲトン７ｏ重量部、エタノール３
０重量部の混合液を３時間かけて連続滴下した。Macromonomer 2 Terminal dicarboxylic acid type MMA macromonomer 100 parts by weight of MMA, 3 parts by weight of thiomalic acid, AlB
6.6 parts by weight of N and 100 parts by weight of methyl ethyl ketone were charged, the atmosphere was replaced with nitrogen, and the liquid temperature was raised to 75°C. Then, while maintaining the N5i product at 75°C, ~IMA
100 parts by weight, 9 parts by weight of thiomalic acid, AlBN6.6
Parts by weight, 7 parts by weight of methyl ethyl getone, 3 parts by weight of ethanol
0 parts by weight of the mixed solution was continuously added dropwise over 3 hours.
滴下後さらに５時間反応させて、得られた反応／＾１０
０重量部をメタノール１００重量部中に除々に投入し、
ジカルボン酸型ＭＭＡマクロモノマーを析出させ、析出
物と溶液とを分離した。分離した析出物を８０°Ｃで真
空乾燥し、精製された固形の末端ジカルボン酸型ＭＭＡ
マクロモノマーを得た。After the dropwise addition, the reaction was further carried out for 5 hours, resulting in the reaction/^10
Gradually add 0 parts by weight to 100 parts by weight of methanol,
The dicarboxylic acid type MMA macromonomer was precipitated, and the precipitate and the solution were separated. The separated precipitate was vacuum dried at 80°C to obtain purified solid terminal dicarboxylic acid type MMA.
A macromonomer was obtained.
マクロモノマー３ 末端ジカルボン酸型ブチルアクリレ
ートマクロモノマー
ローブチルアクリレート１２０重量部、チオリンゴ酸５
．６４重量部、ＡｌＢＮ４．６２重量部、Ｉ・ルエン４
００重量部を仕込み、窒素置換して１ｒｉｌ。Macromonomer 3 120 parts by weight of terminal dicarboxylic acid type butyl acrylate macromonomer robyl acrylate, thiomalic acid 5
．． 64 parts by weight, AlBN 4.62 parts by weight, I. Luene 4
00 parts by weight was added, and the atmosphere was replaced with nitrogen to give 1 ril.
温を８５°Ｃに加熱昇温し、その温度に維持しつつ８時
間反応させた。The temperature was raised to 85°C, and the reaction was carried out for 8 hours while maintaining this temperature.
この反応液を８５°Ｃで真空￥：、燥し、粘性７夜体の
末端ジカルボン酸型ブチルアクリレートマクロモノマー
を得た。The reaction solution was dried in vacuo at 85°C to obtain a viscous hepta-terminated dicarboxylic acid-terminated butyl acrylate macromonomer.
未加硫ゴムシー１〜の製造
表１に示す配合により、ＥＰ系ゴム組組成を混練し、未
加硫ゴムシートを製造した。Production of unvulcanized rubber sheets 1 to 1 EP rubber compositions were kneaded according to the formulations shown in Table 1 to produce unvulcanized rubber sheets.
加硫ゴムシートの製造
先の未加硫ゴムシートを、加硫モールド（１５ＱＩＩＩ
ＩＯＸＩうＱ ＩｎＩＩＩＸ ２１Ｈｎ厚）を使用して
、１８０”Ｃで、１５０に！Ｉ々のプレス圧にて、１０
分間プレスし、加硫ゴムシートを得た。The unvulcanized rubber sheet from the manufacturer of the vulcanized rubber sheet is placed in a vulcanization mold (15QIII
IOXI UQ InIIIX 21Hn thickness) at 180"C, to 150! At various press pressures, 10
The mixture was pressed for a minute to obtain a vulcanized rubber sheet.
基礎１勿性の測定
、ＪＩＳ Ｋ−６３０１に準じて、加硫ゴムシー１〜
の基礎物性を測定した。Measurement of basic 1 elasticity, according to JIS K-6301, vulcanized rubber seams 1~
The basic physical properties of were measured.
加げ【ゴムと未加硫ゴムとの加硫接着
加硫１日後の加硫ゴムシート及び、加硫後７日間２５°
Ｃ×８５％用対湿度のデシケータ−中に放置した加硫ゴ
ムシートについて、それぞれ加硫ゴムシートをはゾ半分
に裁断し、それを前記加硫モールドに入れ、加硫モール
ドにおける残りのはゾ半分の空所に、同一配合の未加硫
ゴムシートを入れ、前記加硫ゴムシーＩ・の製造と同一
条件で加熱加圧し、未加硫ゴムシートを加硫すると共に
、加硫ゴムシートの縁に加硫接着した。Curing [Vulcanized adhesive between rubber and unvulcanized rubber Vulcanized rubber sheet after 1 day of vulcanization and 25° for 7 days after vulcanization
For the vulcanized rubber sheets left in a desiccator with a humidity of 85%, cut each vulcanized rubber sheet in half and place it in the vulcanization mold. An unvulcanized rubber sheet of the same composition is placed in the half space, and heated and pressurized under the same conditions as in the production of the vulcanized rubber sheet I to vulcanize the unvulcanized rubber sheet, and at the same time cure the edges of the vulcanized rubber sheet. It was vulcanized and adhered to.
また同様にして、実施例１の配合による加硫ゴムと比較
例１の配合による未加硫ゴムとの組合わせ及び、比較例
１の配合による加硫ゴムと実施例１の配合による未加硫
ゴムとの組合わせについても加硫接着をした。In addition, in the same manner, vulcanized rubber blended in Example 1 and unvulcanized rubber blended in Comparative Example 1 were combined, and vulcanized rubber blended in Comparative Example 1 and unvulcanized rubber blended in Example 1 were combined. Vulcanized adhesive was also used in combination with rubber.
接着強度の測定
加硫接着したゴムシートを、接着面を中央にしてダンベ
ル３号にて試験片を打抜き、ＪＩＳ Ｉぐ６３０１の
引張り試！狭に準じて引張り、接着面の強度を測定した
。Measurement of adhesive strength A test piece was punched out using a dumbbell No. 3 from the vulcanized rubber sheet with the adhesive side in the center, and subjected to a JIS I6301 tensile test! The strength of the adhesive surface was measured by pulling according to the method.
各実施例及び比較例についての試験結果を表１に示す。Table 1 shows the test results for each example and comparative example.
発明の効果
本発明によれば、ＥＰ系ゴム組成物中に疎水性マクロモ
ノマーを含有しているので、加硫ゴムと未加硫ゴムとの
加硫接着性に優れており、特に高湿度状ｆふでの耐水・
耐湿接着性が大［１１に改善される。Effects of the Invention According to the present invention, since the EP rubber composition contains a hydrophobic macromonomer, it has excellent vulcanization adhesion between vulcanized rubber and unvulcanized rubber, especially in high humidity conditions. Water resistance in F-hood
Moisture-resistant adhesion is greatly improved to [11].
実施例１〜３と比較例１とを比較すると、本発明の実施
例が接着強度が大きいことが判る。また接着性を改善す
るためにアルキルフェノールを含有する比較例２と比べ
ると、１日後の接着強度においては大きな差は認められ
ないが、高湿度雰囲気中に７日間放置した後の接着強度
において本発明の実施例が優れており、本発明の組成物
が湿度による影響を受けに＜＜、耐水・耐湿接着性に１
（れていることか理解できる。Comparing Examples 1 to 3 with Comparative Example 1, it can be seen that the examples of the present invention have higher adhesive strength. Also, compared to Comparative Example 2, which contains alkylphenol to improve adhesion, there is no significant difference in adhesive strength after one day, but the adhesive strength of the present invention after being left in a high humidity atmosphere for 7 days is Examples of the above are excellent, and the composition of the present invention is not affected by humidity and has a water resistance and moisture resistance of 1.
(I can understand why.
実施例４〜７により、疎水性マクロモノマーの）；ト加
景による影響を調べた。これによると、１重量部未満で
は良好な接着強度が得られず、また２０重量部以上では
、過ｆ１の添加に見合う順著な接着性の向上が認められ
ない。In Examples 4 to 7, the influence of the addition of hydrophobic macromonomers was investigated. According to this, if less than 1 part by weight, good adhesive strength cannot be obtained, and if it is more than 20 parts by weight, no significant improvement in adhesiveness commensurate with the addition of excess f1 is observed.
次に実施例８，９及び比較例３．４により加硫剤による
影響を調べたが、本発明は硫黄加硫においても、またペ
ルオキシド加硫においても同様の効果を示すことが判る
。Next, the influence of the vulcanizing agent was investigated using Examples 8 and 9 and Comparative Examples 3 and 4, and it was found that the present invention exhibits similar effects in both sulfur vulcanization and peroxide vulcanization.
加硫ゴムと未加硫ゴムとのいずれか一方に本発明のゴム
組成物を使用した場合における、他のゴム組成物との加
硫接着性を試験し、その結果を表２に示す。When the rubber composition of the present invention was used as either vulcanized rubber or unvulcanized rubber, the vulcanization adhesion with other rubber compositions was tested, and the results are shown in Table 2.
表２
この結果によれば、加硫ゴムと未加硫ゴムとの両方が実
施例１の場合に比べると、接着強度が若干劣ってはいる
ものの、両者が比較例１のものに比べると優れており、
両者が共に本発明の組成１勿であることか好ましいが、
一方だけであっても充分に有効であることが理解できる
。Table 2 According to the results, although the adhesive strength of both vulcanized rubber and unvulcanized rubber is slightly inferior to that of Example 1, both are superior to that of Comparative Example 1. and
It is preferable that both of them are composition 1 of the present invention,
It can be understood that even if only one is used, it is sufficiently effective.
また本発明は、ＥＰ系ゴム組成物を混練する際に疎水性
マクロモノマーを配合することにより得ることができる
ので、作業が簡１１ｉであり、接着力増強のためのパフ
処理等の特別の作業を必要としない。In addition, the present invention can be obtained by blending a hydrophobic macromonomer when kneading the EP rubber composition, so the work is simple and requires special work such as puffing to enhance adhesive strength. does not require.
なお以上の説明においては、ＥＰ系ゴム組成物の、未加
硫ゴムと加硫ゴムとの接着に関してのみ述べたが、加硫
ゴムの間に未加硫ゴムを挾んで加硫接着することによる
加硫ゴム同士の接着に関しても、全く同様に適用するこ
とができることは言うまでもない。In the above explanation, only the adhesion between the unvulcanized rubber and the vulcanized rubber of the EP rubber composition was described, but it is possible to bond the unvulcanized rubber by sandwiching the unvulcanized rubber between the vulcanized rubbers and bonding by vulcanization. It goes without saying that the same method can be applied to adhesion between vulcanized rubbers.
Claims (1)
疎水性マクロモノマーを０．１重量部以上５０重量部未
満含有することを特徴とする、エチレン・プロピレン系
ゴム組成物1 For 100 parts by weight of ethylene/propylene rubber,
An ethylene/propylene rubber composition containing 0.1 parts by weight or more and less than 50 parts by weight of a hydrophobic macromonomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63257669A JP2878694B2 (en) | 1988-10-13 | 1988-10-13 | Ethylene / propylene rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63257669A JP2878694B2 (en) | 1988-10-13 | 1988-10-13 | Ethylene / propylene rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02103247A true JPH02103247A (en) | 1990-04-16 |
| JP2878694B2 JP2878694B2 (en) | 1999-04-05 |
Family
ID=17309460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63257669A Expired - Lifetime JP2878694B2 (en) | 1988-10-13 | 1988-10-13 | Ethylene / propylene rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2878694B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009222469A (en) * | 2008-03-14 | 2009-10-01 | Bridgestone Corp | Conveyor belt and method of manufacturing the same |
| JP2014084363A (en) * | 2012-10-22 | 2014-05-12 | Kaneka Corp | Rubber composition and pneumatic tire using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4848543A (en) * | 1971-10-25 | 1973-07-10 |
-
1988
- 1988-10-13 JP JP63257669A patent/JP2878694B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4848543A (en) * | 1971-10-25 | 1973-07-10 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009222469A (en) * | 2008-03-14 | 2009-10-01 | Bridgestone Corp | Conveyor belt and method of manufacturing the same |
| JP2014084363A (en) * | 2012-10-22 | 2014-05-12 | Kaneka Corp | Rubber composition and pneumatic tire using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2878694B2 (en) | 1999-04-05 |
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