JPH04323245A - Modified acrylic rubber composition and diaphragm for fuel system - Google Patents
Modified acrylic rubber composition and diaphragm for fuel systemInfo
- Publication number
- JPH04323245A JPH04323245A JP14904491A JP14904491A JPH04323245A JP H04323245 A JPH04323245 A JP H04323245A JP 14904491 A JP14904491 A JP 14904491A JP 14904491 A JP14904491 A JP 14904491A JP H04323245 A JPH04323245 A JP H04323245A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic rubber
- composition
- modified acrylic
- monomer
- acrylate
- 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 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920000800 acrylic rubber Polymers 0.000 title claims abstract description 27
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000002033 PVDF binder Substances 0.000 claims abstract description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical group COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000004898 kneading Methods 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 238000003490 calendering Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- -1 2-( n-propoxy)ethyl Chemical group 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- LHEKBWMWMVRJMO-UHFFFAOYSA-N 3-methoxypropyl prop-2-enoate Chemical compound COCCCOC(=O)C=C LHEKBWMWMVRJMO-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WHDGWKAJBYRJJL-UHFFFAOYSA-K ferbam Chemical compound [Fe+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S WHDGWKAJBYRJJL-UHFFFAOYSA-K 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、改質アクリルゴム組成
物及び該組成物でゴム層が成形されてなる燃料系ダイア
フラムに関する。さらに詳しくは、本発明のアクリルゴ
ム組成物は、アクリルゴム（略号ＡＮＭ）にポリフツ化
ビニリデン（略号ＰＶＤＦ）がブレンドされてなり、耐
ガソリン性、耐ガソホール性等とともに耐寒性に優れて
いるものである。そして、本発明の改質アクリルゴム組
成物は、本発明の燃料系ダイアフラムの他に、燃料ホー
ス等のゴム材料として好適なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified acrylic rubber composition and a fuel system diaphragm having a rubber layer formed from the composition. More specifically, the acrylic rubber composition of the present invention is a blend of acrylic rubber (abbreviation: ANM) and polyvinylidene fluoride (abbreviation: PVDF), and has excellent cold resistance as well as gasoline resistance and gasohol resistance. be. The modified acrylic rubber composition of the present invention is suitable as a rubber material for fuel hoses and the like in addition to the fuel system diaphragm of the present invention.
【０００２】下記に、本明細書中で説明を省略した略号
の一覧を示す。[0002] Below is a list of abbreviations whose explanations are omitted in this specification.
【０００３】■ポリマー略号：
ＡＮＭ・・・ アクリルゴム、
ＰＶＤＦ・・・ ポリフツ化ビニリデン、■単量体略号
：
ＥＡ・・・ アクリル酸エチル、
ＭＥＡ・・・ アクリル酸メトキシエチル、ＡＧＥ・・
・ アリルグリシジルエーテル、ＤＰＥ−ＨＡ・・・
ジペンタエリストールヘキサアクリレート、
■ゴム用副資材：
ＴＴＦＥ…ジメチルジチオカルバミン酸第二鉄、ＨＡＦ
…ハイ・アブレイシヨン・フアナス、以下の説明で配合
単位は、特にことわらない限り、重量単位である。また
、「ＰＨＲ」は、ポリマ成分（ゴム成分）１００部に対
する副資材の配合量である。■Polymer abbreviation: ANM... Acrylic rubber, PVDF... Polyvinylidene fluoride, ■Monomer abbreviation: EA... Ethyl acrylate, MEA... Methoxyethyl acrylate, AGE...
・Allyl glycidyl ether, DPE-HA...
Dipentaerythol hexaacrylate, ■Auxiliary materials for rubber: TTFE...ferric dimethyldithiocarbamate, HAF
...High Ablation Huanas In the following explanation, the compounding unit is a weight unit unless otherwise specified. Moreover, "PHR" is the amount of the auxiliary material mixed with respect to 100 parts of the polymer component (rubber component).
【０００４】0004
【従来の技術】昨今、自動車用のガソリン配管に使用さ
れる上記燃料系ダイアフラム等においては、従来にもま
して、耐ガソリン性とともに、耐劣化ガソリン性、さら
には、ガソリン事情から耐ガソホール性等の物性要求が
増大しつつある。[Prior Art] Nowadays, the above-mentioned fuel system diaphragms used in gasoline piping for automobiles have better resistance to gasoline than before, as well as resistance to deterioration of gasoline, and due to the gasoline situation, resistance to gasohol, etc. Physical property requirements are increasing.
【０００５】これに対して、下記構成の改質アクリルゴ
ム組成物が提案されている（特開昭６２−５３３５２号
参照）。In response to this, a modified acrylic rubber composition having the following structure has been proposed (see JP-A-62-53352).
【０００６】「ＡＮＭにＰＶＤＦが、ＡＮＭ／ＰＶＤＦ
＝９０／１０〜７０／３０の重量比でブレンドされてな
り、ＡＮＭの単量体組成が、アクリル酸アルキルエステ
ル、アクリル酸アルコキシ置換アルキルエステル、及び
ＡＮとを単量体主体とするとともに、さらに架橋性単量
体を ０．５〜１０％含有する構成の改質アクリルゴム
組成物。」``PVDF in ANM, ANM/PVDF
= 90/10 to 70/30 weight ratio, and the monomer composition of ANM is mainly composed of acrylic acid alkyl ester, acrylic acid alkoxy-substituted alkyl ester, and AN, and further A modified acrylic rubber composition containing 0.5 to 10% of a crosslinkable monomer. ”
【０００７】[0007]
【発明が解決しようとする課題】しかし、上記構成の改
質アクリルゴム組成物の場合、カレンダー・押出加工性
等に問題を生じた。すなわち、混練後ゴム材料を、カレ
ンダーでシーテイング（ロール分出し）するに際し、未
加硫ゴムがカレンダーロールに密着してロールから剥離
しがたく、所定厚のシート状物（特に２ｍｍ未満の簿肉
のもの）を製造しがたかつた。当該シート状物は、ダイ
ヤフラム等の素材として使用するため、肉厚のバラツキ
が可及的に小さいことが望ましい。また、ゴムホース等
を簿肉層で押し出す際にも、押出ダイにゴム材料が密着
しやすく同様の問題点が発生した。[Problems to be Solved by the Invention] However, in the case of the modified acrylic rubber composition having the above structure, problems such as calendering and extrusion processability occurred. In other words, when the rubber material is sheeted in a calender after kneading (roll separation), the unvulcanized rubber sticks closely to the calender roll and is difficult to peel off from the roll. ) was difficult to manufacture. Since the sheet-like material is used as a material for diaphragms and the like, it is desirable that the variation in wall thickness be as small as possible. Further, when extruding a rubber hose or the like in thin layers, the same problem occurred because the rubber material tends to adhere to the extrusion die.
【０００８】本発明は、上記にかんがみて、混練後のゴ
ム材料のカレンダー・押出加工性の良好な改質アクリル
ゴム組成物を提供することを目的とする。[0008] In view of the above, an object of the present invention is to provide a modified acrylic rubber composition which exhibits good calender/extrusion processability of the rubber material after kneading.
【０００９】本発明の他の目的は、改質アクリルゴム組
成物でゴム層が成形されてなる燃料系ダイアフラムにお
いて、寸法精度良好なものを提供することにある。Another object of the present invention is to provide a fuel system diaphragm having a rubber layer formed from a modified acrylic rubber composition and having good dimensional accuracy.
【００１０】0010
【課題を解決するための手段】本発明は、上記課題を下
記構成により解決するものである。[Means for Solving the Problems] The present invention solves the above problems with the following configuration.
【００１１】ＡＮＭにＰＶＤＦが、ＡＮＭ／ＰＶＤＦ＝
９０／１０〜７０／３０の重量比でブレンドされてなり
、ＡＮＭの単量体組成が、アクリル酸アルキルエステル
、アクリル酸アルコキシ置換アルキルエステル及びＡＮ
を単量体主体とするとともに、さらに、架橋性単量体を
０．１〜１０％含有する構成の改質アクリルゴム組成物
において、前記架橋性単量体が、エポキシ基含有エチレ
ン性不飽和化合物を主成分とし、副成分として４〜６官
能の多官能単量体を、単量体組成中に０．０１〜 ０．
０５ ％含有するものであることを特徴とする。[0011] If PVDF is added to ANM, ANM/PVDF=
The monomer composition of ANM is acrylic acid alkyl ester, acrylic acid alkoxy-substituted alkyl ester, and AN
In the modified acrylic rubber composition, the composition mainly contains epoxy group-containing ethylenically unsaturated The main component is a compound, and a 4- to 6-functional polyfunctional monomer is used as a subcomponent in a monomer composition of 0.01 to 0.
It is characterized by containing 0.05%.
【００１２】0012
【発明の作用・効果】本発明に係る改質アクリルゴム組
成物は、上記のような構成により、混練後のゴム材料の
カレンダー・押出加工性が改善される。Effects of the Invention The modified acrylic rubber composition according to the present invention improves the calender/extrusion processability of the rubber material after kneading due to the above-described structure.
【００１３】從つて、燃料系ダイアフラム、ゴムホース
のような簿肉にカレンダー・押出して成形し、寸法精度
の要求される製品の材料として適用可能になるものであ
る。[0013] After that, it can be calendered and extruded into shapes such as fuel system diaphragms and rubber hoses, and can be used as a material for products that require dimensional accuracy.
【００１４】そして、改質アクリルゴム組成物でゴム層
が成形されてなる燃料系ダイアフラムにおいては、寸法
精度良好なダイアフラムを容易に製造できる。[0014] In a fuel system diaphragm having a rubber layer formed from a modified acrylic rubber composition, a diaphragm with good dimensional accuracy can be easily manufactured.
【００１５】[0015]
（１） 本発明は、ＡＮＭにＰＶＤＦが、ＡＮＭ／ＰＶ
ＤＦ＝９０／１０〜７０／３０の重量比でブレンドされ
てなることを第１の前提要件とする。(1) In the present invention, PVDF is added to ANM, and ANM/PV
The first prerequisite is that they be blended at a weight ratio of DF=90/10 to 70/30.
【００１６】ここで、当該範囲よりＰＶＤＦが過少であ
ると、ＰＶＤＦの配合効果である耐ガソリン性等の向上
が期待できない。また、ＰＶＤＦが過大であると加硫ゴ
ムのゴム的性質（可橈性・ゴム状弾性）が損なわれる。[0016] Here, if the amount of PVDF is too small compared to the above range, improvement in gasoline resistance etc., which is the effect of blending PVDF, cannot be expected. Moreover, if the PVDF is too large, the rubbery properties (flexibility and rubber-like elasticity) of the vulcanized rubber will be impaired.
【００１７】なお、ＰＶＤＦには、平均重合度１００〜
１０００００のものを使用し、ホモポリマーでなくても
、他のビニル系フルオロカーボン、さらには、他のビニ
ル化合物等とのコポリマーも使用可能である。Note that PVDF has an average degree of polymerization of 100 to
100,000, and even if it is not a homopolymer, a copolymer with other vinyl fluorocarbons or other vinyl compounds can also be used.
【００１８】（２） そして本発明は、上記ＡＮＭの単
量体組成は、アクリル酸アルキルエステル、アクリル酸
アルコキシ置換アルキルエステル及びＡＮを単量体主体
とするとともに、さらに、架橋性単量体を０．１〜１０
％含有することを第２の前提要件とする。(2) In the present invention, the monomer composition of the above ANM is mainly composed of acrylic acid alkyl ester, acrylic acid alkoxy-substituted alkyl ester, and AN, and further contains a crosslinkable monomer. 0.1~10
% content is the second prerequisite.
【００１９】ここで、架橋性単量体が０．１％未満では
、ゴムの架橋に時間がかかり過ぎ、１０％を超えると加
硫ゴムが硬くなり過ぎる。If the crosslinking monomer content is less than 0.1%, it will take too long to crosslink the rubber, and if it exceeds 10%, the vulcanized rubber will become too hard.
【００２０】単量体主体となる各単量体の比率は、通常
、アクリル酸アルコキシ置換アルキルエステル：３０〜
７０％、ＡＮ：５〜１４％、アクリル酸アルキルエステ
ル：残部とする。[0020] The ratio of each monomer, which is the main monomer, is usually acrylic acid alkoxy-substituted alkyl ester: 30 to
70%, AN: 5 to 14%, acrylic acid alkyl ester: balance.
【００２１】ここで、アクリル酸アルコキシ置換アルキ
ルエステルが３０％未満では、加硫ゴムに耐劣化ガソリ
ン性を得がたく、７０％を超えると重合させることが困
難となる。ＡＮが５％未満では加硫ゴムに耐劣化ガソリ
ン性を得がたく、１４％を超えると加硫ゴムの耐寒性に
問題を生じやすくなる。[0021] If the alkoxy-substituted alkyl acrylate content is less than 30%, it is difficult to obtain deterioration gasoline resistance in the vulcanized rubber, and if it exceeds 70%, it becomes difficult to polymerize. When AN is less than 5%, it is difficult to obtain deteriorated gasoline resistance in the vulcanized rubber, and when it exceeds 14%, problems tend to occur in the cold resistance of the vulcanized rubber.
【００２２】上記単量体主体となる各単量体としては、
前述の特開昭６２−５３３５２号公報に例示のものを使
用できる。例えば：■アクリル酸アルキルエステルとし
ては、アクリル酸メチル、アクリル酸エチル（ＡＥ）、
アクリル酸ブチル、メタクリル酸メチル、メタクル酸エ
チル、メタクリル酸ブチル等。[0022] Each of the above-mentioned monomers is mainly composed of the following monomers:
The one illustrated in the above-mentioned Japanese Patent Laid-Open No. 62-53352 can be used. For example: ■Acrylic acid alkyl esters include methyl acrylate, ethyl acrylate (AE),
Butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.
【００２３】■アクリル酸アルコキシ置換アルキルエス
テルとしては、アクリル酸２−メトキシエチル（ＭＥＡ
）、アクリル酸２−エトキシエチル、アクリル酸２−（
ｎ−プロポキシ）エチル、アクリル酸３−メトキシプロ
ピル等。■As the alkoxy-substituted alkyl acrylate, 2-methoxyethyl acrylate (MEA
), 2-ethoxyethyl acrylate, 2-(
n-propoxy)ethyl, 3-methoxypropyl acrylate, etc.
【００２４】（３） 本発明は、架橋性単量体成分が、
エポキシ基含有エチレン性不飽和化合物を主成分とする
とともに４〜６官能の多官能単量体を副成分として含有
することを特徴とする。(3) In the present invention, the crosslinkable monomer component is
It is characterized by containing an epoxy group-containing ethylenically unsaturated compound as a main component and a 4- to 6-functional polyfunctional monomer as a subcomponent.
【００２５】■ここで、エポキシ基含有エチレン性不飽
和化合物を架橋性単量体成分の主成分とするのは、それ
らの化合物が、成形時の金型腐食を促進させないためで
ある。(2) The reason why the epoxy group-containing ethylenically unsaturated compound is used as the main component of the crosslinking monomer component is that these compounds do not accelerate mold corrosion during molding.
【００２６】当該化合物としては、アリルグリシジルエ
ーテル（ＡＧＥ）、アクリル酸グリシジル、メタクリル
酸グリシジル等を挙げることができるが、特に、ＡＧＥ
が、スコーチ安定性等の見地から望ましい。[0026] Examples of the compound include allyl glycidyl ether (AGE), glycidyl acrylate, glycidyl methacrylate, etc. In particular, AGE
However, it is desirable from the viewpoint of scorch stability.
【００２７】■上記多官能単量体は、単量体組成中に０
．０１〜 ０．０５ ％を含有する。■ The above polyfunctional monomer contains 0 in the monomer composition.
．． Contains 01-0.05%.
【００２８】ここで官能数が４未満では、または、多官
能単量体の含有量が０．０１％未満では、本発明の効果
、即ち、混練後のゴム材料の加工性の向上（ロ−ルから
の剥離が容易）がそれぞれ期待できない。また、官能数
が６を超え、または、多官能単量体の含有量が０．０５
％を超えると、カレンダー・押出時の表面肌が良好でな
くなる（波打つ）。この表面肌の不良は、ダイアフラム
・ゴムホース等の製品品質に悪影響を与える。Here, if the functional number is less than 4, or if the content of the polyfunctional monomer is less than 0.01%, the effect of the present invention, that is, the improvement in the processability of the rubber material after kneading (low- (Easy to peel off from the base) cannot be expected. In addition, the number of functionalities exceeds 6, or the content of polyfunctional monomers is 0.05.
If it exceeds %, the surface texture during calendering and extrusion will not be good (wavy). This poor surface texture adversely affects the quality of products such as diaphragms and rubber hoses.
【００２９】また、多官能単量体としては、ペンタエリ
スリトールテトラ（メタ）アクリレート、ジペンタエリ
スリトールペンタ（メタ）アクリレート、ジペンタエリ
スリトールヘキサ（メタ）アクリレート等を挙げること
ができるが、特に、ジペンタエリスリトールヘキサアク
リレート（ＤＰＥ−ＨＡ）が望ましい。[0029] Examples of the polyfunctional monomer include pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., but in particular dipentaerythritol hexa(meth)acrylate, etc. Erythritol hexaacrylate (DPE-HA) is preferred.
【００３０】（４） 本発明の改質アクリルゴム組成物
に使用するＡＮＭの製造は、慣用の方法により行う。即
ち、上記単量体組成物を、乳化剤、重合開始剤等ともに
、水中に乳化させ重合させて得れれる乳化重合体を、塩
析、乾燥させて行う。このとき重合率は、通常、９０％
以上とする。(4) ANM used in the modified acrylic rubber composition of the present invention is produced by a conventional method. That is, the above-mentioned monomer composition is emulsified in water together with an emulsifier, a polymerization initiator, etc., and an emulsion polymer obtained by polymerization is salted out and dried. At this time, the polymerization rate is usually 90%
The above shall apply.
【００３１】このＡＮＭはＰＶＤＦと慣用の方法、例え
ば、ロール、バンバリミキサー等により混合する。[0031] The ANM is mixed with the PVDF in a conventional manner, for example, using a roll, Banbury mixer, or the like.
【００３２】こうして得た改質ＡＮＭ（ポリマーブレン
ド）は、通常のゴム配合物に添加される副資材、即ち、
カーボンブラツク、ステアリン酸、可塑剤、加硫系薬剤
等を配合して混練しゴム材料とする。該混練後のゴム材
料は、カレンダーまたは押出機等により、薄層にロール
分出し、又は、押出す。このとき、後述の実施例・比較
例で示すごとく、ロール分出し性が良好であり、かつ、
表面肌も良好である。The modified ANM (polymer blend) thus obtained can be used as an auxiliary material added to ordinary rubber compounds, namely:
Carbon black, stearic acid, plasticizer, vulcanizing agent, etc. are mixed and kneaded to make a rubber material. The rubber material after kneading is rolled or extruded into thin layers using a calendar or an extruder. At this time, as shown in the Examples and Comparative Examples described later, the roll dispensing property is good, and
The surface skin is also good.
【００３３】（５） 本発明のダイアフラムは、上記改
質アクリルゴム組成物でゴム層が成形されてなるもので
ある。(5) The diaphragm of the present invention has a rubber layer formed from the above-mentioned modified acrylic rubber composition.
【００３４】そして、例えば、図１に示す基布１の両面
にゴム層３、３が形成されてなる両面ゴムタイプのダイ
アフラムの場合、基布１の両面に配合生ゴムをトッピン
グし、所定形状に打ち抜いてブランクを用意し、圧縮加
硫成形により製造する。本発明のダイアフラムは、両面
ゴムタイプに限られず、片面ゴムタイプ（図２）、総ゴ
ムタイプ（図３）にも適用可能である。For example, in the case of a double-sided rubber type diaphragm in which rubber layers 3, 3 are formed on both sides of the base fabric 1 shown in FIG. A blank is prepared by punching and manufactured by compression vulcanization molding. The diaphragm of the present invention is not limited to a double-sided rubber type, but can also be applied to a single-sided rubber type (FIG. 2) and a full rubber type (FIG. 3).
【００３５】こうして製造したダイアフラム５は、燃料
ポンプ（図４）や燃料噴射装置の燃料調節弁（図５）に
、組みつけられて使用される。The diaphragm 5 manufactured in this manner is used by being assembled into a fuel pump (FIG. 4) or a fuel control valve (FIG. 5) of a fuel injection device.
【００３６】即ち、図４においては、ダイアフラム５の
外周部が、ポンプケース７の上ケース７ａ及び下ケース
７ｂのフランジ部間に挟持されて、また、ダイアフラム
５の中央部が、従動棒９と連結された上下従動板１１ａ
、１１ｂで挟持されて組み付けられている。そして、下
従動板１１ｂの下面と下ケース７ｂの底面との間に圧縮
コイルばね１３が配されている。That is, in FIG. 4, the outer periphery of the diaphragm 5 is sandwiched between the flanges of the upper case 7a and lower case 7b of the pump case 7, and the center portion of the diaphragm 5 is held between the driven rod 9 and the flange portions of the lower case 7b. Connected upper and lower driven plates 11a
, 11b and assembled. A compression coil spring 13 is disposed between the lower surface of the lower driven plate 11b and the bottom surface of the lower case 7b.
【００３７】図５においては、図４と同様、弁ケース１
５の上ケース１５ａ及び下ケース１５ｂの各フランジ部
に挟持されて、中央部が上下作動板１７ａ、１７ｂに挟
持されて組みつけられている。そして、上作動板１７ａ
の上面と上ケース１５ａの天井面との間には圧縮コイル
ばね１９が配されている。In FIG. 5, as in FIG. 4, the valve case 1
It is sandwiched between the flanges of the upper case 15a and lower case 15b of No. 5, and the center portion is sandwiched between the vertical operation plates 17a and 17b. Then, the upper operating plate 17a
A compression coil spring 19 is arranged between the upper surface of the upper case 15a and the ceiling surface of the upper case 15a.
【００３８】[0038]
【試験例】以下、本発明の効果を確認するために、行な
つた試験例について説明をする。[Test Examples] Test examples conducted to confirm the effects of the present invention will be explained below.
【００３９】（１） 表−１の上段に示す単量体組成の
ものから重合したＡＮＭとＰＶＤＦとを、下記配合処方
に基づいて副資材を配合し、混練後のゴム材料を、ロー
ル分出しして、シート成形の可否を判定するとともに、
分出しシートの波打ちの有無を目視判定した。(1) ANM and PVDF polymerized from the monomer composition shown in the upper row of Table 1 are blended with auxiliary materials based on the following formulation, and the rubber material after kneading is separated by roll. In addition to determining whether or not sheet forming is possible,
The presence or absence of undulation of the dispensed sheet was visually determined.
【００４０】表−１に示す結果から、本発明の改質アク
リルゴム組成物は、副資材を配合して混練後の材料を、
ロール分出しする際等における加工性が良好であること
がわかる。[0040] From the results shown in Table 1, the modified acrylic rubber composition of the present invention has the following properties:
It can be seen that the workability during roll dispensing etc. is good.
【００４１】なお、参考的に、■配合物のカーボンブラ
ツク分散性の目視判定結果、■ポリマーブレンドのムー
ニー粘度（ ＪＩＳ Ｋ ６３００ ）を参考的に記す
。[0041] For reference, (1) Visual evaluation results of carbon black dispersibility of the blend and (2) Mooney viscosity (JIS K 6300) of the polymer blend are listed below.
【００４２】[0042]
【表１】[Table 1]
【図１】本発明を適用する両面ゴムタイプのダイアフラ
ムのモデル断面図である。FIG. 1 is a cross-sectional view of a model of a double-sided rubber type diaphragm to which the present invention is applied.
【図２】同じく片面ゴムタイプのダイアフラムのモデル
断面図である。FIG. 2 is a cross-sectional view of a model of a single-sided rubber type diaphragm.
【図３】同じく総ゴムタイプのダイアフラムのモデル断
面図である。FIG. 3 is a cross-sectional view of a model of a diaphragm of the same all-rubber type.
【図４】本発明のダイアフラムを装着可能な燃料ポンプ
の概略断面図である。FIG. 4 is a schematic cross-sectional view of a fuel pump to which the diaphragm of the present invention can be installed.
【図５】同じく燃料噴射装置の調節弁の概略断面図であ
る。FIG. 5 is a schematic cross-sectional view of a control valve of the fuel injection device.
１ 基布、 ３ ゴム層。 1 Base fabric, 3. Rubber layer.
Claims (5)
フツ化ビニリデン（略号ＰＶＤＦ）が、ＡＮＭ／ＰＶＤ
Ｆ＝９０／１０〜７０／３０の重量比でブレンドされて
なり、前記ＡＮＭの単量体組成が、アクリル酸アルキル
エステル、アクリル酸アルコキシ置換アルキルエステル
及びアクリロニトリル（略号ＡＮ）を単量体主体とする
とともに、さらに架橋性単量体を０．１〜１０ｗｔ％含
有する構成の改質アクリルゴム組成物において、前記架
橋性単量体が、エポキシ基含有エチレン性不飽和化合物
を主成分とし、、副成分として、４〜６官能の多官能単
量体を前記単量体組成中に０．０１〜 ０．０５ｗｔ％
含有するものであることを特徴とする改質アクリルゴム
組成物。Claim 1: Acrylic rubber (abbreviation ANM) and polyvinylidene fluoride (abbreviation PVDF) are added to ANM/PVD.
F is blended at a weight ratio of 90/10 to 70/30, and the monomer composition of the ANM is mainly composed of acrylic acid alkyl ester, acrylic acid alkoxy-substituted alkyl ester, and acrylonitrile (abbreviation AN). In addition, in the modified acrylic rubber composition further containing 0.1 to 10 wt% of a crosslinkable monomer, the crosslinkable monomer is mainly composed of an epoxy group-containing ethylenically unsaturated compound, As a subcomponent, 0.01 to 0.05 wt% of a 4- to 6-functional polyfunctional monomer is added to the monomer composition.
A modified acrylic rubber composition comprising:
ペンタエリスリトールテトラ（メタ）アクリレート、ジ
ペンタエリスリトールペンタ（メタ）アクリレート、ジ
ペンタエリスリトールヘキサ（メタ）アクリレートの群
から選択される１種又は２種以上のものであることを特
徴とする改質アクリルゴム組成物。2. Claim 1, wherein the polyfunctional monomer is
A modified acrylic rubber characterized by being one or more selected from the group of pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Composition.
レン性不飽和化合物が、アリルグリシジルエーテル、ア
クリル酸グリシジル、メタクリル酸グリシジルの群から
選択される１種又は２種以上のものであることを特徴と
する改質アクリルゴム組成物。3. In claim 1, the epoxy group-containing ethylenically unsaturated compound is one or more selected from the group of allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate. Modified acrylic rubber composition.
キシ置換アルキルエステルがアクリル酸２−メトキシエ
チル（略号ＭＥＡ）であり、かつ、それらの組成比が、
ＡＮ：５〜１５ｗｔ％、ＭＥＡ：３０〜７０ｗｔ％であ
ることを特徴とする改質アクリルゴム組成物。4. In claim 1, the alkoxy-substituted alkyl acrylate is 2-methoxyethyl acrylate (abbreviated as MEA), and their composition ratio is:
A modified acrylic rubber composition characterized in that AN: 5 to 15 wt% and MEA: 30 to 70 wt%.
成物でゴム層が成形されてなる燃料系ダイアフラム。5. A fuel system diaphragm having a rubber layer formed from the modified acrylic rubber composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3149044A JP3030317B2 (en) | 1991-02-25 | 1991-06-21 | Modified acrylic rubber composition and fuel diaphragm |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2897091 | 1991-02-25 | ||
| JP3-28970 | 1991-02-25 | ||
| JP3149044A JP3030317B2 (en) | 1991-02-25 | 1991-06-21 | Modified acrylic rubber composition and fuel diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04323245A true JPH04323245A (en) | 1992-11-12 |
| JP3030317B2 JP3030317B2 (en) | 2000-04-10 |
Family
ID=26367123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3149044A Expired - Fee Related JP3030317B2 (en) | 1991-02-25 | 1991-06-21 | Modified acrylic rubber composition and fuel diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3030317B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19534977A1 (en) * | 1995-09-20 | 1997-03-27 | Metzeler Gimetall Ag | Low-permeation composite material for retaining gas or vapour |
| JP2012224765A (en) * | 2011-04-20 | 2012-11-15 | Jsr Corp | Composition for thermally conductive sheet |
| WO2013027783A1 (en) | 2011-08-25 | 2013-02-28 | Daikin Industries, Ltd. | Diaphragm |
-
1991
- 1991-06-21 JP JP3149044A patent/JP3030317B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19534977A1 (en) * | 1995-09-20 | 1997-03-27 | Metzeler Gimetall Ag | Low-permeation composite material for retaining gas or vapour |
| JP2012224765A (en) * | 2011-04-20 | 2012-11-15 | Jsr Corp | Composition for thermally conductive sheet |
| WO2013027783A1 (en) | 2011-08-25 | 2013-02-28 | Daikin Industries, Ltd. | Diaphragm |
| US10000619B2 (en) | 2011-08-25 | 2018-06-19 | Daikin Industries, Ltd. | Diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3030317B2 (en) | 2000-04-10 |
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