WO1993022586A1 - Gasket for automotive engine transmission - Google Patents

Gasket for automotive engine transmission Download PDF

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Publication number
WO1993022586A1
WO1993022586A1 PCT/JP1993/000571 JP9300571W WO9322586A1 WO 1993022586 A1 WO1993022586 A1 WO 1993022586A1 JP 9300571 W JP9300571 W JP 9300571W WO 9322586 A1 WO9322586 A1 WO 9322586A1
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WO
WIPO (PCT)
Prior art keywords
gasket
monomer
parts
weight
automobile engine
Prior art date
Application number
PCT/JP1993/000571
Other languages
French (fr)
Japanese (ja)
Inventor
Mamoru Ohmori
Takashi Namba
Tsukasa Horichi
Masayasu Tomoda
Tsuyoshi Noguchi
Kazuhisa Matsumoto
Etsuo Minamino
Original Assignee
Daikin Industries, Ltd.
Uchiyama Manufacturing Corp.
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Daikin Industries, Ltd., Uchiyama Manufacturing Corp. filed Critical Daikin Industries, Ltd.
Priority to EP9393911954A priority Critical patent/EP0592691A4/en
Publication of WO1993022586A1 publication Critical patent/WO1993022586A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025Crosslinking or vulcanising agents; including accelerators
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/04Polymer mixtures characterised by other features containing interpenetrating networks

Definitions

  • the present invention relates to an automobile engine and a transmission gasket.
  • Automotive gaskets are used in automotive internal combustion engines to seal the cover attached to the cylinder head, and can be used to clearly determine the suitability of the material due to the heat load and vibration generated during operation. is there. That is, the cold resistance of the engine at cold start and the heat resistance at high speed load are required.
  • the temperature difference between the intake and exhaust sides or ⁇ depends on the mounting angle on the vehicle. If there is oil leakage, it is a high risk of fire due to dripping on the exhaust pipe.
  • An object of the present invention is homogeneously disperse of f and fluoropolymer and acrylic elastomers primary, phase separation does not give a vulcanized rubber, taking advantage of the respective characteristics, heat resistance, mechanical strength during the heat and resistance to engine oil Paburingu
  • Another object of the present invention is to provide a gasket for an automobile engine and a transmission which is excellent in quality.
  • CS permanent distortion
  • ATF Automatic Transmission
  • LLC Long Life Coolant
  • a filler is added to 100 parts by weight of a polymer obtained by dissolving or swelling an amorphous fluoropolymer in an acryl-based monomer and then subjecting the monomer to polymerization to obtain a polymer.
  • a car engine and a transmission gasket obtained from a bridge composition containing L00 parts by weight and a crosslinking agent 0.1 to 10 parts by weight o
  • the present inventors have conducted intensive studies in order to uniformly disperse the fluorine-containing polymer and acrylyl elastomer and to maintain the compatibility of the heat treatment for vulcanization. After dissolving or swelling in the swelling monomer, the polymer obtained by polymerizing the acrylyl monomer is blended with a filler and a crosslinking agent. In oil bubbling, it has been found that gaskets for automobile engines and transmissions with far superior performance that cannot be predicted from a simple blend of a fluoropolymer and an acrylyl elastomer can be obtained.
  • gasket for an automobile engine and transmission according to the present invention has excellent permanent distortion, ATF resistance, LLC resistance, and durability.
  • Examples of the amorphous fluorine-containing polymer capable of dissolving or swelling in the acryl monomer used in the present invention include, for example, vinylidenefluoridonehexaphenolylpropylene, vinylidenefluoride Ztetrafluoroethylenoxyhexafluoropropylene , Vinylidene fluoride copolymers such as vinylidene fluoride copolymers such as chlorofluoroethylene, tetrafluoroethylene Z propylene, hexafluoropropylene Z ethylene, phenolic (alkyl vinyl ether) (Including those containing a plurality of ether bonds) / olefin-based co-union, fluorine-containing silicone rubber, phenolic phosphazene rubber, and the like, and among these, vinylidenefluoride Z hexafluoro Propylene, vinylidene fluoride / Tetrafluoroethylene / hexafluoro
  • the type of acrylic monomer is not limited, but includes mono- or polyfunctional ones, one or more types are used, and the polyfunctional monomer is preferably used in a small amount in combination with the monofunctional monomer.
  • Preferred examples of these are, for example, methyl methacrylate (MMA :), ethyl methacrylate (EMA :), butyl methacrylate (BMA), 2-hydroxyethyl methacrylate (HEMA :), glycidyl methacrylate (GMA :), 2-Methoxyxetyl methacrylate (MEM A) 3- (Trimethoxysilyl) propyl methacrylate (MSPM), 2- (phenylphosphoryl) ethyl methacrylate (phenyl-P), 2-hydroxy-3- (S-naphthoxy) propyl Methacrylate (HNPM), N-phenyl N- (2-hydroxy-3-methacryloxy) propylglycine (NPG-GMA),
  • CH 2 C (CH 3 ) COOCH 2 CF 3 (3FMA).
  • CH 2 CFCOOCH 2 CF 2 CF 3 (5FFA).
  • a small amount of acrylonitrile, 2-chloroethylvinyl ether, monochlorovinyl acetate, methylvinyldichlorosilane, or the like may be used in the monomer for the purpose of modification.
  • the amount of the polyfunctional monomer is preferably 1 to 20 parts per 100 parts (parts by weight, hereinafter the same) of the monofunctional monomer.
  • the ratio between the amorphous fluorine-containing polymer and the acryl monomer can be appropriately determined, but it is usually preferable to use the latter in the range of 5 to L000 parts per 100 parts of the former.
  • the above-mentioned fluoropolymer is dissolved or swelled in an acryl monomer, and then is subjected to polymerization to polymerize it.
  • the polymerization is carried out in the presence of a polymerization initiation source, and further, a polymerization inhibitor is used.
  • a polymerization inhibitor is used.
  • Initiation sources include light and heat, as well as polymerization of benzoyl baroxide, azoisobutyronitrile (AIBN), camphorquinone (CQ), 91-fluorenone, tributylborane (TBB), benzophenone, etc.
  • Initiators include reducing agents such as dimethylaminoethyl methacrylate (DMAEMA) and dimethyl-p-toluidine (DMPT), polymerization inhibitors such as hydroquinone and hydroquinone methyl ester, and transfer agents such as lauryl menoleic butane. Can be.
  • DMAEMA dimethylaminoethyl methacrylate
  • DMPT dimethyl-p-toluidine
  • transfer agents such as lauryl menoleic butane.
  • transfer agents such as lauryl menoleic butane.
  • IPN Inter-penetrating Polymer Network
  • a polymer substance is polymerized in advance, and a monomer for forming a guest polymer is injected into the polymer substance, or the polymer is immersed in a solution containing the monomer and injected, and thereafter, heating or light irradiation or the like is performed.
  • Other methods are also used:
  • Examples of the filler used in the present invention include reinforcing materials such as carbon black, silica, clay, diatomaceous earth, talc, and calcium carbonate.
  • the amount of the filler is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.1 part by weight, a sufficient reinforcing effect cannot be obtained. If the amount exceeds 100 parts by weight, rubber-like properties are lost.
  • examples of the crosslinking agent used in the present invention include, for example, peroxides, polyols, polyamines, and the like used for crosslinking vinylidene fluoride-based fluororubber.
  • Perhexa 2.5B manufactured by NOF CORPORATION, Peroxide
  • triaryl isocyanurate TA IC
  • bisphenol AF bisphenol AF
  • N.N'-dicinnamylidene-1,6-hexadiamine and the like.
  • the crosslinking agent is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.1 part by weight, the degree of crosslinking is insufficient, and if it exceeds 10 parts by weight, the rubber-like properties tend to be lost.
  • a compound containing a vinyl group or an aryl group can be used.
  • compounding agents such as antioxidants, processing aids, scorch inhibitors, ozone deterioration inhibitors, ultraviolet absorbers, flame retardants, and plasticizers may be used as necessary.
  • a gasket for an automobile engine or transmission obtained by dissolving or swelling a fluorinated polymer in an acrylic monomer and then polymerizing this monomer is obtained from a simple blend of a fluorinated polymer and an acrylyl elastomer. Compared with those, it has superior performance in heat resistance, mechanical strength during heat, and engine oil bubbling far beyond prediction.
  • gasket for an automobile engine and transmission according to the present invention has a permanent set, Excellent in ATF, LLC resistance and durability.
  • composition used in the present invention has a slightly higher viscosity than ordinary simple blend rubber-based materials.
  • low-temperature decomposable (50 to 130 ° C) peroxide and a polyfunctional compound (referred to as a co-crosslinking agent) The composition thus prepared can be applied on-site for a gasket and vulcanized in a hot air atmosphere of 60 to 150.
  • Parts and% indicate parts by weight and% by weight, respectively.
  • An automotive gasket was prepared from a composition comprising the components shown in Table 1 below.
  • a gasket for an automobile was prepared in the same manner as in Example 1 using a composition obtained by blending each composition of Comparative Example 2 and Comparative Example 3 at a weight ratio of 50:50.
  • G702 manufactured by Daikin Industries, vinylidene fluoride Z hexafluoropropylene copolymer, FAU-014 Y: copolymer of G702 / nBuAc / l, 6-HXA (70/27/3) NBuAc: n-butyl acrylate, 1,6-HXA: 1,6-hexanediol diacrylate.
  • Nowgard 445 is an antioxidant from Uniroyal Chem.
  • Tb Tensile strength
  • the gasket for an automobile engine and transmission according to the present invention has excellent heat resistance, mechanical strength when heated, and engine oil pub Vung. Further, the gasket for an automobile engine and transmission according to the present invention is excellent in permanent distortion, ATF resistance, LLC resistance, and durability.

Abstract

A gasket for automotive engine transmission, made from a cross-linking composition comprising 100 parts by weight of a polymer prepared by dissolving or swelling a noncrystalline fluoropolymer in an acrylic monomer and polymerizing the monomer, 0.1 to 100 parts by weight of a filler, and 0.1 to 10 parts by weight of a cross-linking agent. This gasket is excellent in mechanical strength and resistance to engine oil bubbling at high temperatures and also in compression set, resistances to automatic transmission fluid and long-life coolant, and durability.

Description

明 細 書 自動車エンジン、 トランスミッション用ガスケット  Description Gaskets for automobile engines and transmissions
(技術分野) (Technical field)
本発明は自動車エンジン、 トランスミッション用ガスケットに関する。  The present invention relates to an automobile engine and a transmission gasket.
(背景技術)  (Background technology)
自動車用ガスケットは自動車用内燃機関において、 シリンダ一へッドに装着さ れるカバーを密封するのに用いられ、 運転時に発生する熱負荷と振動により材質 的にも適否が明確に把握可能なものである。 即ち、 エンジンのコールドスタート 時の耐寒性、 高速負荷時の耐熱性が問われ、 さらにはエンジンの構造上、 吸気側、 排気側における温度差或 ヽは車両への搭載角度によりエンジン油或いはトランス ミッシヨン油の漏れがあっては排気管上に滴下することで火災になる危険性の高 い部位である。  Automotive gaskets are used in automotive internal combustion engines to seal the cover attached to the cylinder head, and can be used to clearly determine the suitability of the material due to the heat load and vibration generated during operation. is there. That is, the cold resistance of the engine at cold start and the heat resistance at high speed load are required. In addition, due to the structure of the engine, the temperature difference between the intake and exhaust sides or 或 depends on the mounting angle on the vehicle. If there is oil leakage, it is a high risk of fire due to dripping on the exhaust pipe.
従来、 このような自動車エンジン、 トランスミッション用ガスケットはァクリ ルエラストマー或いは含フッ素ポリマーより作成されていたが、 前者は耐熱性、 熱時の機械的強度、 耐エンジン油バブリングにおいて劣るという欠点を有してい た。 後者は耐熱性、 耐エンジン油パブリングは良好であるが、 熱時の機械的強度 に著しく劣るという欠点があった。  Conventionally, such gaskets for automobile engines and transmissions have been made of acryl elastomers or fluoropolymers, but the former have the drawback of being inferior in heat resistance, mechanical strength during heating, and engine oil bubbling resistance. Was. The latter has good heat resistance and good engine oil publishing, but has the drawback that the mechanical strength when heated is extremely poor.
そこで上記ァクリルエラストマーと含フッ素ポリマーの両者を混練プレンドし て自動車エンジン、 トランスミッション用ガスケットを作成したところ、 予想に 反して耐熱性、 熱時の機械的強度、 耐エンジン油バブリングの全ての性能におい て著しく劣ることが判明した。 このことは後記比較例から明らかである。  Therefore, we prepared a gasket for an automobile engine and transmission by kneading and blending both the acryl elastomer and the fluorine-containing polymer. Unexpectedly, all of the performances of heat resistance, mechanical strength during heat, and engine oil bubbling were expected. Turned out to be significantly inferior. This is clear from the comparative examples described later.
本発明の目的は含フッ素ポリマー及びアクリルエラストマ一とを均質に分散さ f せ、 相分離しない加硫ゴムを得、 それぞれの特性を活かし、 耐熱性、 熱時の機械 的強度及び耐エンジン油パブリングに優れた自動車エンジン、 トランスミツショ ン用ガスケットを提供することにある。 An object of the present invention is homogeneously disperse of f and fluoropolymer and acrylic elastomers primary, phase separation does not give a vulcanized rubber, taking advantage of the respective characteristics, heat resistance, mechanical strength during the heat and resistance to engine oil Paburingu Another object of the present invention is to provide a gasket for an automobile engine and a transmission which is excellent in quality.
また本発明の目的は永久歪 (C S) 、 耐 A T F (Automatic Transmission Fuel) 、耐 L L C (Long Life Coolant) 、耐久性にも優れた自動車ェンジ ン、 トランスミッション用ガスケットを提供することにある。 It is also an object of the present invention to provide a permanent distortion (CS), ATF (Automatic Transmission) Fuel), anti-LLC (Long Life Coolant), highly durable automobile engine, and transmission gasket.
本発明は非晶質の含フッ素ポリマーをァクリル系モノマー中に溶解もしくは膨 潤させて、次いでこのモノマーを重合に付して高分子化して得られる重合物 100 重量部に対して、充填材 0. 1〜: L00重量部、架橋剤 0. 1〜10重量部を含有する架 橋用組成物より得られる自動車ェンジン、 トランスミッション用ガスケットに係 る o  In the present invention, a filler is added to 100 parts by weight of a polymer obtained by dissolving or swelling an amorphous fluoropolymer in an acryl-based monomer and then subjecting the monomer to polymerization to obtain a polymer. ... 1 to: a car engine and a transmission gasket obtained from a bridge composition containing L00 parts by weight and a crosslinking agent 0.1 to 10 parts by weight o
本発明者らは、含フッ素ボリマーとァクリルエラストマ一の均質な分散を行わ せ更に加硫のための加熱処理 の相溶性を保たせるために鋭意研究を重ねた結果、 含フッ素ポリマーをァクリゾレモノマーに溶解或いは膨潤させた後、 ァクリルモノ マーに重合を施して得られた重合物に、 充填材及び架橋剤を配合した架橋用組成 物より耐熱性、熱時の機械的強度、耐エンジン油バブリングにおいて、 単なる含 フッ素ポリマーとァクリルエラストマ一の混練ブレンド品からは予測できないよ うな遥かに卓越した性能を有する自動車エンジン、 トランスミッシヨン用ガスケ ットが得られることを見い出した。  The present inventors have conducted intensive studies in order to uniformly disperse the fluorine-containing polymer and acrylyl elastomer and to maintain the compatibility of the heat treatment for vulcanization. After dissolving or swelling in the swelling monomer, the polymer obtained by polymerizing the acrylyl monomer is blended with a filler and a crosslinking agent. In oil bubbling, it has been found that gaskets for automobile engines and transmissions with far superior performance that cannot be predicted from a simple blend of a fluoropolymer and an acrylyl elastomer can be obtained.
また本発明の自動車エンジン、 トランスミッション用ガスケットは永久歪、耐 ATF、 耐 L L C、耐久性にも優れている。  Further, the gasket for an automobile engine and transmission according to the present invention has excellent permanent distortion, ATF resistance, LLC resistance, and durability.
本発明において使用するァクリルモノマーに溶解もしくは膨潤し得る非晶質の 含フッ素ポリマーとしては、例えばビニリデンフルオラィドンへキサフノレォロプ ロピレン系、 ビニリデンフルォライド Zテトラフルォロェチレンノへキサフルォ 口プロピレン系、 ビニリデンフルォライド クロ口トリフルォロェチレン系等の ビニリデンフルォライド系の共重合体、 テトラフルォロエチレン Zプロピレン系、 へキサフルォロプロピレン Zェチレン系、 フノレオ口(アルキルビニルエーテル)(複 数個のエーテル結合を含むものも包含する)/ォレフィン系の共童合体、 フルォ 口シリコンゴム、 フノレオ口ホスファゼンゴムなどが挙げられ、 又これらのうち、 ビニリデンフルオラィド Zへキサフルォロプロピレン系、 ビニリデンフルォラ ィド /テトラフルォロエチレン/へキサフルォロプロピレン系、 ビニリデンフル ォライド Zクロ口トリフルォロエチレン系のポリマーが好ましい。 本発明において非晶質とは DS C (Differential S canning Colorimeter)の ピークで実質的に融点が観察されないものを言う。 Examples of the amorphous fluorine-containing polymer capable of dissolving or swelling in the acryl monomer used in the present invention include, for example, vinylidenefluoridonehexaphenolylpropylene, vinylidenefluoride Ztetrafluoroethylenoxyhexafluoropropylene , Vinylidene fluoride copolymers such as vinylidene fluoride copolymers such as chlorofluoroethylene, tetrafluoroethylene Z propylene, hexafluoropropylene Z ethylene, phenolic (alkyl vinyl ether) (Including those containing a plurality of ether bonds) / olefin-based co-union, fluorine-containing silicone rubber, phenolic phosphazene rubber, and the like, and among these, vinylidenefluoride Z hexafluoro Propylene, vinylidene fluoride / Tetrafluoroethylene / hexafluoropropylene-based polymer, vinylidene fluoride Z-trifluoroethylene-based polymer is preferred. In the present invention, the term "amorphous" refers to an amorphous material in which the melting point is not substantially observed at the peak of DSC (Differential Scanning Colorimeter).
本発明においてアクリルモノマーとしては種類は制限されないが、 単または多 官能性のものが含まれ、 一種又は 2種以上が用いられ、 多官能性モノマーは単官 能性モノマーと併用で少量用いるのが好ましい。 これらの例として好ましくは、 例えばメチルメタクリレート(MM A:)、 ェチルメタクリレート(EMA:)、 ブチル メタクリレート(BMA)、 2—ヒドロキシェチルメタクリレート(HEMA:)、 グ リシジルメタクリレート(GMA:)、 2—メ トキシェチルメタクリレート(MEM A) 3—(トリメ トキシシリル)プロピルメタクリレート(MSPM)、 2—(フエ ニルホスホリル)ェチルメタクリレート(phenyl— P)、 2—ヒドロキシー 3—(S 一ナフトキシ)プロピルメタクリレート(HNPM)、 N—フエ二ルー N—(2—ヒ ドロキシー 3—メタクリ口キシ)プロピルグリシン(NPG— GMA)、 エチレン グリコールジメタクリレート(EDMA又は 1G)、 ジエチレングリコールジメタ クリレート(DiEDMA又は 2G:)、 トリエチレングリコールジメタクリレート(T riEDMA又は 3G)、 テトラエチレングリコールジメタクリレート(TEDMA 又は 4G)、 1,4一ブタンジオールジメタクリレート(1,4一 BuDMA)、 1,3—ブ タンジオールジメタクリレート(1.3-BuDMA)、 2,2—ビス 〔4一(2—ヒドロ キシー 3—メタクリロキシプロボキシ)フエニル〕 プロパン(Bis— GMA:)、 2,2 —ビス(4一メタクリロキシフエニル)プロパン(BPDMA)、 2.2—ビス(4ーメ タクリロキシエトキシフエ二ノレ)プロパン(Bis— MEPP)、 2,2—ビス(4ーメ タクリロキシポリエトキンフエニル)プロパン(Bis— MP EPP)、 ジ(メタクリ 口キシェチル)トリメチルへキサメチレンジウレタン(U DMA). トリメチロー ルプロパントリメタクリレート(TMPT:)、  In the present invention, the type of acrylic monomer is not limited, but includes mono- or polyfunctional ones, one or more types are used, and the polyfunctional monomer is preferably used in a small amount in combination with the monofunctional monomer. preferable. Preferred examples of these are, for example, methyl methacrylate (MMA :), ethyl methacrylate (EMA :), butyl methacrylate (BMA), 2-hydroxyethyl methacrylate (HEMA :), glycidyl methacrylate (GMA :), 2-Methoxyxetyl methacrylate (MEM A) 3- (Trimethoxysilyl) propyl methacrylate (MSPM), 2- (phenylphosphoryl) ethyl methacrylate (phenyl-P), 2-hydroxy-3- (S-naphthoxy) propyl Methacrylate (HNPM), N-phenyl N- (2-hydroxy-3-methacryloxy) propylglycine (NPG-GMA), ethylene glycol dimethacrylate (EDMA or 1G), diethylene glycol dimethacrylate (DiEDMA or 2G: ), Triethylene glycol dimethacrylate (TriEDMA or 3G), tetraethylene Recall dimethacrylate (TEDMA or 4G), 1,4-butanediol dimethacrylate (1,4-BuDMA), 1,3-butanediol dimethacrylate (1.3-BuDMA), 2,2-bis [4-1 (2 —Hydroxy 3-methacryloxypropoxy) phenyl] propane (Bis—GMA :), 2,2-bis (4-methacryloxyphenyl) propane (BPDMA), 2.2—bis (4-methacryloxyethoxyphene) Nore) propane (Bis-MEPP), 2,2-bis (4-methacryloxypolyethoxyquinphenyl) propane (Bis-MP EPP), di (methacrylic quichetyl) trimethylhexamethylene diurethane (U DMA). Trimethylol propane trimethacrylate (TMPT :),
C.H2=C(CH3)COOCH2CF3 (3FMA).CH 2 = C (CH 3 ) COOCH 2 CF 3 (3FMA).
(4FMA)、 (4FMA),
CH2=C(CH3)COOCH2CF2CF3 (5FMA) CH 2 = C (CH 3 ) COOCH 2 CF 2 CF 3 (5FMA)
CH2=C(CH3)COOCH2(CF2)zCF3 (7FMA)、 CH 2 = C (CH 3 ) COOCH 2 (CF 2 ) z CF 3 (7FMA),
CH2=C(CH3)COOCH2(CF2)3CF2H (8FMA)、 これらの対応する各ァクリレート、 各 一フルォロアクリレートを例示すること ができる。 CH 2 = C (CH 3 ) COOCH 2 (CF 2 ) 3 CF 2 H (8FMA), Each of these corresponding acrylates and each fluoroacrylate can be exemplified.
上記 α—フルォロァクリレートとしては例えば  Examples of the above α-fluoroacrylate include
CH2=CFCOOCH2CF2CF2H (4FFA)、 CH 2 = CFCOOCH 2 CF 2 CF 2 H (4FFA),
CH2=CFCOOCH2CF2CF3 (5FFA). CH 2 = CFCOOCH 2 CF 2 CF 3 (5FFA).
CH2=CFCOOCH2(CF2)3CF2H (8FFA)、 CH 2 = CFCOOCH 2 (CF 2 ) 3 CF 2 H (8FFA),
CH2=CFCOOCH¾(CF2)5CF2H (12FFA) CH 2 = CFCOOCH ¾ (CF 2 ) 5 CF 2 H (12FFA)
等を例示することができる。 And the like.
又、 モノマー中に改質の意味でァグリロニトリル、 2—クロルェチルビニルェ 一テル、 モノクロル酢酸ビニル、 メチルビ二ルジクロルシランなどを少量用いて も良い。 多官能性モノマーを用いる場合、 その使用量は好適には単官能性モノマ 一 100部 (重量部、以下同様) に対して多官能性モノマーを 1〜20部とするのが 良い。  In addition, a small amount of acrylonitrile, 2-chloroethylvinyl ether, monochlorovinyl acetate, methylvinyldichlorosilane, or the like may be used in the monomer for the purpose of modification. When a polyfunctional monomer is used, the amount of the polyfunctional monomer is preferably 1 to 20 parts per 100 parts (parts by weight, hereinafter the same) of the monofunctional monomer.
本発明において非晶質の含フッ素ポリマーとァクリルモノマーの割合は適宜決 定することができるが、通常は前者 100部に対して後者を 5〜: L000部の範囲で 用いるのが好ましい。  In the present invention, the ratio between the amorphous fluorine-containing polymer and the acryl monomer can be appropriately determined, but it is usually preferable to use the latter in the range of 5 to L000 parts per 100 parts of the former.
本発明においては上記含フッ素ポリマーをァクリルモノマー中に溶解もしくは 膨濶せしめ、次いでこれを重合に付して高分子化するが、 その際重合開始源の存 在下に行い、更に、重合禁止剤、還元剤、移勤剤等を加えることもできる。 重合 開始源としては光、熱のほか、ベンゾィルバーォキサイド、 ァゾイソプチロニト リル (A I BN)、 カンファーキノン(CQ)、 9一フルォレノン、 トリブチルボラ ン(TBB)、ベンゾフエノン等の重合開始剤を、還元剤としてはジメチルァミノ ェチルメタクリレート(DMAEMA)、 ジメチルー p—トルイジン(DMPT)等 を、重合禁止剤としてはヒドロキノン、 ヒドロキノンメチルエステル等を、移動 剤としてはラウリルメノレ力ブタン等を挙げることができる。 そして、本発明の組 成物を架橋せしめることにより、 また多官能ァクリル系モノマーを使用すること により I PN (Inter— penetrating Polymer Network)が形成されるが、 ここで I PNとは本来 2種の鎖状のボリマーを液体状態 (溶液でも可)で混合し、 両方又はいずれか一方を架橋させ、互いに分子鎖を絡み合わせた形で形成される ポリマーである。 I P N化方法を本発明に適用する場合、 通常以下の方法が用い られる。 即ち、 予め高分子物質を重合しておき、 これにゲスト高分子を形成する モノマーを注入するか、 前記モノマーを含む溶液に前記重合物を浸潰し、 注入し、 しかる後、 加熱又は光照射等の操作により高分子化し、充填材、 架橋剤等を混合 した後架橋させる方法が挙げられる。 その他の方法も使用する:;とができる。 本発明において用いられる充填材としては例えばカーボンブラック、 シリカ、 クレー、珪藻土、 タルク、 炭酸カルシウム等の補強材を例示できる。 充填材の量 は重合物 100重量部に対して 0. 1〜: 100重量部が好ましい。 0. 1重量部未満では十分 な補強効果が得られず、 100重量部を越えるとゴム的性質を失う。 In the present invention, the above-mentioned fluoropolymer is dissolved or swelled in an acryl monomer, and then is subjected to polymerization to polymerize it.In this case, the polymerization is carried out in the presence of a polymerization initiation source, and further, a polymerization inhibitor is used. , A reducing agent, a transfer agent, and the like. Initiation sources include light and heat, as well as polymerization of benzoyl baroxide, azoisobutyronitrile (AIBN), camphorquinone (CQ), 91-fluorenone, tributylborane (TBB), benzophenone, etc. Initiators include reducing agents such as dimethylaminoethyl methacrylate (DMAEMA) and dimethyl-p-toluidine (DMPT), polymerization inhibitors such as hydroquinone and hydroquinone methyl ester, and transfer agents such as lauryl menoleic butane. Can be. By cross-linking the composition of the present invention and using a polyfunctional acryl-based monomer, an IPN (Inter-penetrating Polymer Network) is formed. Mix the chain polymer in the liquid state (or solution), A polymer formed by crosslinking both or any one of them and entangled with each other in molecular chains. When the IPN method is applied to the present invention, the following method is usually used. That is, a polymer substance is polymerized in advance, and a monomer for forming a guest polymer is injected into the polymer substance, or the polymer is immersed in a solution containing the monomer and injected, and thereafter, heating or light irradiation or the like is performed. A method of polymerizing by the above operation, mixing a filler, a cross-linking agent, and the like, and then cross-linking. Other methods are also used: Examples of the filler used in the present invention include reinforcing materials such as carbon black, silica, clay, diatomaceous earth, talc, and calcium carbonate. The amount of the filler is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.1 part by weight, a sufficient reinforcing effect cannot be obtained. If the amount exceeds 100 parts by weight, rubber-like properties are lost.
次に本発明で用いられる架橋剤としてはビニリデンフルオラィド系フッ素ゴム の架橋に用いられる例えばパーオキサイド、 ポリオール、 ポリアミン等力挙げら れ具体的にはパーへキサ 2. 5B (日本油脂製、 パーオキサイド)、 トリァリルイソ シァヌレート(TA I C)、 ビスフエノール A F、 N. N'—ジシンナミリデン一 1, 6—へキサジァミン等が挙げられる。 架橋剤は重合物 100重量部に対して 0. 1〜 10重量部が好ましい。 0. 1重量部未満では架橋度が不十分で、 10重量部を越える とゴム的性質を失う傾向がみられる。  Next, examples of the crosslinking agent used in the present invention include, for example, peroxides, polyols, polyamines, and the like used for crosslinking vinylidene fluoride-based fluororubber.Specifically, Perhexa 2.5B (manufactured by NOF CORPORATION, Peroxide), triaryl isocyanurate (TA IC), bisphenol AF, N.N'-dicinnamylidene-1,6-hexadiamine and the like. The crosslinking agent is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.1 part by weight, the degree of crosslinking is insufficient, and if it exceeds 10 parts by weight, the rubber-like properties tend to be lost.
更に必要に応じて架橋促進剤として窒素又はリンを含む有機第 3級又は第 4級 化合物など、受酸剤としては 2価金属の酸化物又は水酸化物など、 また架橋助剤 として複数個のビニル基、 又はァリル基を含む化合物などを用いることができる。 その他、必要に応じて老化防止剤、加工助剤、 スコーチ防止剤、 オゾン劣化防止 剤、 紫外線吸収剤、 難燃剤、 可塑剤等の配合剤を用いても良い。  Further, if necessary, an organic tertiary or quaternary compound containing nitrogen or phosphorus as a cross-linking accelerator, a divalent metal oxide or hydroxide as an acid acceptor, and a plurality of cross-linking aids as a cross-linking aid. A compound containing a vinyl group or an aryl group can be used. In addition, compounding agents such as antioxidants, processing aids, scorch inhibitors, ozone deterioration inhibitors, ultraviolet absorbers, flame retardants, and plasticizers may be used as necessary.
本発明において含フッ素ポリマーをァクリル系モノマー中に溶解もしくは膨潤 させて、次いでこのモノマーを重合させることにより得られる自動車エンジン、 トランスミッション用ガスケットは単なる含フッ素ポリマーとァクリルエラスト マーのブレンド品より得られるものに比し、耐熱性、 熱時の機械的強度、耐ェン ジン油バブリングにおいて予測を遥かに越える優れた性能を有する。  In the present invention, a gasket for an automobile engine or transmission obtained by dissolving or swelling a fluorinated polymer in an acrylic monomer and then polymerizing this monomer is obtained from a simple blend of a fluorinated polymer and an acrylyl elastomer. Compared with those, it has superior performance in heat resistance, mechanical strength during heat, and engine oil bubbling far beyond prediction.
また本発明の自動車エンジン、 トランスミッション用ガスケットは永久歪、 耐 ATF、 耐 LLC、耐久性にも優れている。 Further, the gasket for an automobile engine and transmission according to the present invention has a permanent set, Excellent in ATF, LLC resistance and durability.
また本発明で用いられる組成物は通常の単純ブレンドゴム系材料より粘度が若 干大きく、例えば低温分解型 (50〜130°C)パーォキサイドと多官能性化合物 (共架 橋剤とする)を配合した組成物をガスケッ卜用として現場施工しておき、 60〜150 の熱風雰囲気下で加硫させることもできる。  Further, the composition used in the present invention has a slightly higher viscosity than ordinary simple blend rubber-based materials. For example, low-temperature decomposable (50 to 130 ° C) peroxide and a polyfunctional compound (referred to as a co-crosslinking agent) The composition thus prepared can be applied on-site for a gasket and vulcanized in a hot air atmosphere of 60 to 150.
(発 を実施するための最良の形態)  (Best mode for carrying out departure)
以下に実施例及び比較例を挙げて説明する。 尚、部及び%は重量部及び重量% を示す。  Hereinafter, an example and a comparative example will be described. Parts and% indicate parts by weight and% by weight, respectively.
実施例 1及び比較例 〜 3 Example 1 and Comparative Examples ~ 3
下記表 1に示す成分よりなる組成物より自動車用ガスケットを作成した。  An automotive gasket was prepared from a composition comprising the components shown in Table 1 below.
比較例 4 Comparative Example 4
比較例 2と比較例 3の各組成物を重量比で 50 : 50の割合でブレンドした組 成物を用いて実施例 1と同様にして自動車用ガスケットを作成した。  A gasket for an automobile was prepared in the same manner as in Example 1 using a composition obtained by blending each composition of Comparative Example 2 and Comparative Example 3 at a weight ratio of 50:50.
表 1において  In Table 1
G 702:ダイキン工業製、 ビニリデンフルォライド Zへキサフルォロプロピレ ン共重合体、 F AU-014 Y: G 702/nBuAc/l, 6-HXA (70/27/3) の共重合体、 nBuAc: n—プチルァクリレート、 1,6-HXA: 1,6—へキサン ジオールジァクリレートである。 ナウガード 445は Uniroyal Chem社製の老 化防止剤を示す。 G702: manufactured by Daikin Industries, vinylidene fluoride Z hexafluoropropylene copolymer, FAU-014 Y: copolymer of G702 / nBuAc / l, 6-HXA (70/27/3) NBuAc: n-butyl acrylate, 1,6-HXA: 1,6-hexanediol diacrylate. Nowgard 445 is an antioxidant from Uniroyal Chem.
表 1 table 1
次に上記各組成物の物性の評価を下記に従い行った。 結果を表 2に示す c Next, the physical properties of each of the above compositions were evaluated as follows. The results are shown in Table 2 c
(1) 引張強さ (Tb) : J I S 6301に準拠した。 (1) Tensile strength (Tb): Based on JIS 6301.
(2) 引裂強さ (TR) : J I S 6301に準拠した。  (2) Tear strength (TR): Based on JIS 6301.
(3) 永久歪 (CS) : J I S 6301に準拠した。 (4) ゲーマン低温捩り試験 ·: J I S 6301にて冷媒イソプロピルアルコール U P A) を使用して測定した。 (3) Permanent set (CS): Conforms to JIS 6301. (4) Gehman low-temperature torsion test ·: Measured using isopropyl alcohol (UPA) in JIS 6301.
(5)耐エンジン油バブリング:日産ェクストラセーブ X (7.5W-30) を使用 して測定した。 150°Cx72hr  (5) Engine oil bubbling resistance: Measured using Nissan Xtra Save X (7.5W-30). 150 ° Cx72hr
(6)耐 ATF : 150°Cx72hr キャスルフルイドデキシロン 2  (6) ATF resistance: 150 ° Cx72hr Castle Fluid Dexilone 2
(7)耐 L L C: 120r 48hr ドョタ純正 L L Cと水 (1: I vol比)  (7) L L C: 120r 48hr Dota genuine L L C and water (1: I vol ratio)
(8)耐熱性: 175°Cx500hr  (8) Heat resistance: 175 ° Cx500hr
(9)耐久性: 5 9 mmの断面のガスケットのカバーの溝寸法が 5 x $匪のもの について試験した。  (9) Durability: A gasket cover with a cross section of 59 mm and a groove dimension of 5 x $ was tested.
(a)初期組付面圧 面圧 30kgfZcm2以上 圧縮量 30% (a) Initial assembly surface pressure Surface pressure 30 kgfZcm 2 or more Compressed amount 30%
(b)初期シール性 面圧 2kgfZcm2以上 圧縮量 30% (b) Initial sealing surface pressure 2kgfZcm 2 or more Compression amount 30%
( c )亀裂耐久 溝深さ 6 mZmに、高さ 9 mZni、 出代 3 mZm  (c) Crack endurance Groove depth 6 mZm, height 9 mZni, outgrowth 3 mZm
50%圧縮 15(TCx24hr 5サイクル 50% compression 15 (TCx24hr 5 cycles
(d)連続高速耐久 30%圧縮 150°Cx500hr  (d) Continuous high-speed durability 30% compression 150 ° Cx500hr
( e) 熱衝搫漏れ耐久 30%圧縮  (e) Heat shock leakage durability 30% compression
(150で xl5hr) + (-30°Cx 9hr) 20サイクル  (150xxl5hr) + (-30 ° Cx9hr) 20 cycles
オイル充填、無圧状態で熱衝撃を加える。 漏れはミクロチェックの変色によるォ ィルにじみを観察した。 Apply thermal shock with oil filling and no pressure. Leakage was observed by bleeding due to discoloration of the micro check.
表 2 Table 2
(産業上の利用可能性) (Industrial applicability)
本発明の自動車エンジン、 トランスミッション用ガスケットは優れた耐熱性、 熱時の機械的強度及び耐ェンジン油パブ Vングを有する。 また本発明の自動車ェ ンジン、 トランスミッション用ガスケットは永久歪、 耐 ATF、 耐 LLC、耐 久性にも優れている。  The gasket for an automobile engine and transmission according to the present invention has excellent heat resistance, mechanical strength when heated, and engine oil pub Vung. Further, the gasket for an automobile engine and transmission according to the present invention is excellent in permanent distortion, ATF resistance, LLC resistance, and durability.

Claims

請求の範囲 The scope of the claims
(1)非晶質の含フッ素ポリマーをァクリル系モノマー中に溶解もしくは膨瀾さ せて、 次いでこのモノマーを重合に付して高分子化して得られる重合物 100重量 部に対して、充填材 0.1〜100重量部、架橋剤 0.1〜10重量部を含有する架橋用 組成物より得られる自動車エンジン、 トランスミッション甩ガスケット。  (1) An amorphous fluorine-containing polymer is dissolved or swollen in an acryl-based monomer, and then the monomer is subjected to polymerization to obtain a polymer to obtain a polymer. An automobile engine and transmission gasket obtained from a crosslinking composition containing 0.1 to 100 parts by weight and 0.1 to 10 parts by weight of a crosslinking agent.
(2)非晶質の含フッ素ポリマーがビニリデンフルォライド Zへキサフルォロブ ロピレン系、 ビニリデンフルォライド zテ卜ラフルォロエチレン/へキサフルォ 口プロピレン系、 ビニリデンフルオラィド Zクロロトリフルォ口ェチレン系の共 重合体、 テトラフルォロエチレン/プロピレン系、 へキサフルォロプロピレンノ エチレン系、 フルォロ(アルキルビニルエーテル) (複数個のエーテル結合を含む ものも包含する) Zォレフィン系の共重合体、 フルォ口シリコンゴム又はフルォ ロホスファゼンゴムである請求の範囲第 1項記載の自動車ェンジン、 トランスミ ッシヨン用ガスケット。  (2) Amorphous fluorine-containing polymer is vinylidene fluoride Z hexafluoropropylene, vinylidene fluoride z tetrafluoroethylene / hexafluoro propylene, vinylidene fluoride Z chlorotrifluorene Copolymers such as tetrafluoroethylene / propylene, hexafluoropropyleneethylene, fluoro (alkyl vinyl ether) (including those containing a plurality of ether bonds) Z-olefin copolymers, 2. The gasket for automobile engines and transmissions according to claim 1, wherein said gasket is silicone rubber or fluorophosphazene rubber.
(3)非晶質の含フッ素ポリマーがビニリデンフルオラィドノへキサフルォロブ 口ピレン系、 ビニリデンフルォラィド /テトラフルォロェチレン/へキサフルォ 口プロピレン系、 ビニリデンフルオラィド Zクロ口トリフルォロエチレン系の共 重合体である請求の範囲第 2項記載の自動車エンジン、 トランスミッション用ガ スケット。  (3) Amorphous fluorine-containing polymer is vinylidenefluoridonohexafluorob pyrene, vinylidenefluoride / tetrafluoroethylen / hexafluor propylene, vinylidenefluoride Z 3. The gasket for an automobile engine and transmission according to claim 2, wherein the gasket is an ethylene-based copolymer.
(4) アタリルモノマーとして単官能性ァクリルモノマー及び多官能性ァクリル モノマーが併用して用いられる請求の範囲第 1項記載の自動車エンジン、 トラン スミッション用ガスケット。  (4) The gasket for an automobile engine or transmission according to claim 1, wherein a monofunctional acrylyl monomer and a polyfunctional acrylyl monomer are used in combination as the ataryl monomer.
(5)単官能性モノマー 100重量部に対して多官能性モノマーを 1〜20重量部用 いる請求の範囲第 4項記載の自動車エンジン、 トランスミッション用ガスケット。  (5) The gasket for an automobile engine and transmission according to claim 4, wherein the polyfunctional monomer is used in an amount of 1 to 20 parts by weight per 100 parts by weight of the monofunctional monomer.
(6 )非晶質の含フッ素ポリマー 100重量部に対してアクリルモノマーを 5〜 1000部用いる請求の範囲第 1項記載の自動車エンジン、小ランスミッション用ガ スケット。  (6) The gasket for an automobile engine and a small transmission according to claim 1, wherein the acrylic monomer is used in an amount of 5 to 1000 parts per 100 parts by weight of the amorphous fluoropolymer.
(7)充填材がカーボンブラック、 シリカ、 クレー、珪藻土、 タルク又は炭酸力 ルシゥムである請求の範囲第 1項記載の自動車ェンジン、 トランスミッション用 ガスケット。 (7) The automobile engine and the transmission according to claim 1, wherein the filler is carbon black, silica, clay, diatomaceous earth, talc or carbonated calcium. gasket.
(8 ) 架橋剤がパーォキサイド、 ポリオール又はポリアミンである請求の範囲第 1項記載の自動車エンジン、 トランスミッション用ガスケット。  (8) The gasket for an automobile engine or transmission according to claim 1, wherein the crosslinking agent is a peroxide, a polyol or a polyamine.
PCT/JP1993/000571 1992-04-30 1993-04-28 Gasket for automotive engine transmission WO1993022586A1 (en)

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Application Number Priority Date Filing Date Title
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JP4/139872 1992-04-30

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Publication Number Publication Date
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6317983A (en) * 1986-07-09 1988-01-25 Nippon Reinz Co Ltd Gasket
JPH02245046A (en) * 1989-03-17 1990-09-28 Nok Corp Rubber composition
JPH02276809A (en) * 1988-09-06 1990-11-13 Daikin Ind Ltd Solid polymeric substance, its production and use thereof
JPH02308841A (en) * 1989-05-24 1990-12-21 Japan Synthetic Rubber Co Ltd Fluororubber composition
JPH0356771A (en) * 1989-07-25 1991-03-12 Nippon Reinz Co Ltd Gasket for engine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6317983A (en) * 1986-07-09 1988-01-25 Nippon Reinz Co Ltd Gasket
JPH02276809A (en) * 1988-09-06 1990-11-13 Daikin Ind Ltd Solid polymeric substance, its production and use thereof
JPH02245046A (en) * 1989-03-17 1990-09-28 Nok Corp Rubber composition
JPH02308841A (en) * 1989-05-24 1990-12-21 Japan Synthetic Rubber Co Ltd Fluororubber composition
JPH0356771A (en) * 1989-07-25 1991-03-12 Nippon Reinz Co Ltd Gasket for engine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0592691A4 *

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