JP7157464B2 - ゴム組成物および加工方法、並びにそれを用いたゴムホースおよび製造方法 - Google Patents
ゴム組成物および加工方法、並びにそれを用いたゴムホースおよび製造方法 Download PDFInfo
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- JP7157464B2 JP7157464B2 JP2019559147A JP2019559147A JP7157464B2 JP 7157464 B2 JP7157464 B2 JP 7157464B2 JP 2019559147 A JP2019559147 A JP 2019559147A JP 2019559147 A JP2019559147 A JP 2019559147A JP 7157464 B2 JP7157464 B2 JP 7157464B2
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- rubber
- parts
- cross
- kneaded
- hose
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- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 claims description 2
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- UIGULSHPWYAWSA-UHFFFAOYSA-N 3-amino-4-[(2-methylpropan-2-yl)oxy]-4-oxobutanoic acid;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)C(N)CC(O)=O UIGULSHPWYAWSA-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- BFGOGLKYJXQPJZ-UHFFFAOYSA-N 4-methylhept-1-ene Chemical compound CCCC(C)CC=C BFGOGLKYJXQPJZ-UHFFFAOYSA-N 0.000 description 1
- WNEYWVBECXCQRT-UHFFFAOYSA-N 5-methylhept-1-ene Chemical compound CCC(C)CCC=C WNEYWVBECXCQRT-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- OAKHANKSRIPFCE-UHFFFAOYSA-L calcium;2-methylprop-2-enoate Chemical compound [Ca+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O OAKHANKSRIPFCE-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical group 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical group [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
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- B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
- B29C48/151—Coating hollow articles
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- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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Landscapes
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- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
Claims (15)
- 重量部で、
分岐ポリエチレンの含有量a:0<a≦100部であり、
EPMとEPDMの含有量b:0≦b<100部であるゴムマトリックス(a+b=100)と、
ゴムマトリックス100重量部に対して、架橋剤1.5~8部、補強充填剤50~200部、可塑剤10~100部を含む必須成分と、を含むゴム組成物であって、前記分岐ポリエチレンは、エチレンホモポリマーを含み、分岐度が80~105分岐/1000炭素、重量平均分子量が25.0万~40.0万、ムーニー粘度ML(1+4)125℃が2以上であることを特徴とするゴムホースを製造するためのゴム組成物。 - ゴムマトリックス100重量部のうち、分岐ポリエチレンの含有量a:10≦a≦100重量部であり、EPMとEPDMの含有量b:0≦b≦90部であり、分岐ポリエチレンは、エチレンホモポリマーであって、分岐度が82~102分岐/1000炭素であることを特徴とする請求項1に記載のゴム組成物。
- 前記架橋剤は、硫黄または過酸化物架橋剤の少なくとも一つを含み、前記過酸化物架橋剤は、ジ-tert-ブチルパーオキサイド、ジクミルパーオキサイド、tert-ブチルクミルパーオキサイド、1,1-ジ-tert-ブチルパーオキシ-3,3,5-トリメチルシクロヘキサン、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキシン-3、ビス(tert-ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、tert-ブチルパーオキシベンゾエート、tert-ブチルパーオキシ-2-エチルヘキシルカーボネートの少なくとも一つを含むことを特徴とする請求項1に記載のゴム組成物。
- 前記補強充填剤は、カーボンブラック、炭酸カルシウム、焼成クレー、ケイ酸マグネシウム、ケイ酸アルミニウム、炭酸マグネシウム、タルク粉、珪藻土の少なくとも一つを含むことを特徴とする請求項1に記載のゴム組成物。
- 前記可塑剤は、ステアリン酸、パインタール油、モーター油、ナフテン油、パラフィン油、クマロン、パラフィン、液体ポリイソブチレン、ジオクチルセバケートの少なくとも一つを含むことを特徴とする請求項1に記載のゴム組成物。
- ゴムマトリックス100重量部に対して、重量部で、架橋助剤0.2~8部、金属酸化物2~15部、安定剤1~3部、ポリエチレングリコール1~5部、加硫促進剤0~3部を含む補助成分をさらに含み、
前記架橋助剤は、トリアリルシアヌレート、トリアリルイソシアヌレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、トリアリルトリメリテート、トリメチロールプロパントリメタクリレート、N,N’-m-フェニレンビスマレイミド、ビスフルフリリデンアセトン、1,2-ポリブタジエン、不飽和カルボン酸金属塩および硫黄の少なくとも一つを含み、
前記金属酸化物は、酸化亜鉛、酸化マグネシウム、酸化カルシウムの少なくとも一つを含み、
前記安定剤は、2,2,4-トリメチル-1,2-ジヒドロキノリンポリマー(RD)、6-エトキシ-2,2,4-トリメチル-1,2-ジヒドロキノリン(AW)、2-メルカプトベンズイミダゾール(MB)の少なくとも一つを含み、
前記ポリエチレングリコールは、2000、3400、または4000の分子量を有するポリエチレングリコールの少なくとも一つを含み、
前記加硫促進剤は、2-チオールベンゾチアゾール、ジベンゾチアゾールジスルフィド、テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、ジ-n-ブチルジチオカルバミン酸亜鉛、N-シクロヘキシル-2-ベンゾチアジルスルフェンアミド、N,N-ジシクロヘキシル-2-ベンゾチアジルスルフェンアミド、ビスマレイミド、エチレンチオ尿素の少なくとも一つを含むことを特徴とする請求項1に記載のゴム組成物。 - (1)密閉式混練機の温度と回転子の回転数を設定し、用いられるゴム組成物中の架橋系以外の成分を順次に密閉式混練機に投入して混練した後、架橋系を添加し、混練後にゴムを排出させる工程であって、架橋系は架橋剤を含み、架橋助剤および加硫促進剤の少なくとも一つをさらに含んでもよい工程と、
(2)工程(1)で得られた混練ゴムをオープンロールで薄通ししてシートとして取り出し、放置する工程と、
(3)金型のキャビティ内に混練ゴムを充填し、プレス加硫機で加熱加圧加硫した後、離型することで加硫ゴムが得られる工程と、
を含むことを特徴とする請求項1~6のいずれか一項に記載のゴム組成物の加工方法。 - 使用されるゴム混合物が請求項1~6のいずれか一項に記載のゴム組成物からなることを特徴とするゴムホース。
- (1)まず、架橋系以外のゴム組成物の成分を重量部に応じて順次に密閉式混練機に添加して混練した後、架橋系を添加し均一に混練してから排出させ、混練ゴムを得て、混練ゴムをオープンロールで薄通ししてからシートとして取り出し、架橋系は架橋剤を含み、架橋助剤および加硫促進剤の少なくとも一つをさらに含んでもよいゴム混練工程と、
(2)コールドフィード押出機を用いて、マンドレル上にゴム層を押し出してホースブランクを得て、蒸気加硫を行ってから冷却し、マンドレルから取り外し、トリミングし、検査し、入庫してゴムホースを得る押出と成形工程と、
を含むことを特徴とする請求項8に記載のゴムホースの製造方法。 - 内側ゴム層および外側ゴム層の少なくとも一つが請求項1~6のいずれか一項に記載のゴム組成物からなることを特徴とする自動車用ラジエータゴムホース。
- (1)密閉式混練機の温度および回転子の回転数を適切に設定し、架橋系以外のゴム組成物の成分を重量部に応じて順次に密閉式混練機に添加して混練した後、架橋系を添加し均一に混練してから排出させ、混練ゴムを得て、混練ゴムをオープンロールで薄通ししてからシートとして取り出し、架橋系は架橋剤を含み、架橋助剤および加硫促進剤の少なくとも一つをさらに含んでもよいゴム混練工程と、
(2)コールドフィード押出機を用いて、内側ゴム層を押し出した後、内側ゴム層に繊維強化層を編み、さらに、外側ゴム層を押し出してホースブランクを得て、加硫のためにホースブランクを切断する押出と成形工程と、
(3)マンドレルをホースブランクに挿入し、蒸気加硫を行ってから冷却し、マンドレルから取り外し、トリミングし、検査し、入庫して自動車用ラジエータゴムホースを得る加硫工程と、
を含むことを特徴とする請求項10に記載の自動車用ラジエータゴムホースの製造方法。 - 内側ゴム層および外側ゴム層の少なくとも一つが請求項1~6のいずれか一項に記載のゴム組成物からなることを特徴とする空調ゴムホース。
- (1)密閉式混練機の温度および回転子の回転数を適切に設定し、架橋系以外のゴム組成物の成分を重量部に応じて順次に密閉式混練機に添加して混練した後、架橋系を添加し均一に混練してから排出させ、混練ゴムを得て、混練ゴムをオープンロールで薄通ししてからシートとして取り出し、架橋系は架橋剤を含み、架橋助剤および加硫促進剤の少なくとも一つをさらに含んでもよいゴム混練工程と、
(2)マンドレルを用意し、マンドレル上にナイロンアロイライニングを押し出し、内側ゴム層を押し出して、繊維強化層を編み、次いで外側ゴム層を押し出す押出と成形工程と、
(3)テープ巻付加硫を行い、テープの巻付を解き、マンドレルから取り外して切断することで空調ゴムホースを得る加硫工程と、
を含むことを特徴とする請求項12に記載の空調ゴムホースの製造方法。 - 内側ゴム層および外側ゴム層の少なくとも一つが請求項1~6のいずれか一項に記載のゴム組成物からなることを特徴とするゴムホース組立体。
- (1)オープンロールまたは密閉式混練機を用いて、前記内側ゴム層および外側ゴム層の原料をそれぞれ内層混練ゴムおよび外層混練ゴムに加工し、検出に合格してから、不純物を濾過によって除去するゴム混練工程と、
(2)コールドフィード押出機を用いて内側ゴム層を押し出し、さらに、内側ゴム層の外面にアラミド繊維層を編み、最後に、外側ゴム層押出機により外層混練ゴムを押し出し、前記アラミド繊維層の外面を被覆してホースブランクを形成するホースブランクの成形工程と、
(3)前記ホースブランクをホースモールドのマンドレル上に装着し、蒸気加硫缶に置き、蒸気で0.9MPaに加圧し、175℃に加温し、25分間加硫して加硫ゴムホースを得る加硫工程と、
(4)前記加硫ゴムホースを洗浄して裁断した後、各ホースの両端にプレオープンしたクランプフープを接着してゴムホース組立体を得るクランプフープの装着工程と、
を含むことを特徴とする請求項14に記載のゴムホース組立体の製造方法。
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