JPS63291930A - Method for modifying surface of molded fluorine-containing elastomer product - Google Patents
Method for modifying surface of molded fluorine-containing elastomer productInfo
- Publication number
- JPS63291930A JPS63291930A JP62125030A JP12503087A JPS63291930A JP S63291930 A JPS63291930 A JP S63291930A JP 62125030 A JP62125030 A JP 62125030A JP 12503087 A JP12503087 A JP 12503087A JP S63291930 A JPS63291930 A JP S63291930A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing elastomer
- vulcanization
- page
- molded product
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 42
- 239000011737 fluorine Substances 0.000 title claims abstract description 42
- 239000000806 elastomer Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims description 43
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001973 fluoroelastomer Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- -1 magnesium oxide Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OMFMOEOGTAYVMW-UHFFFAOYSA-N CC=C.C=C.C=C(F)F.F.F.F.F.F.F.F.F.F.F Chemical compound CC=C.C=C.C=C(F)F.F.F.F.F.F.F.F.F.F.F OMFMOEOGTAYVMW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UZCPNEBHTFYJNY-UHFFFAOYSA-N benzyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1CP(C=1C=CC=CC=1)C1=CC=CC=C1 UZCPNEBHTFYJNY-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- PPCXFTKZPBHXIW-UHFFFAOYSA-N ethyl ethanesulfonate Chemical compound CCOS(=O)(=O)CC PPCXFTKZPBHXIW-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は含フッ素エラストマー成形品の新規な表面改質
方法に関するものである。さらに詳しくいえば、本発明
は、含フッ素エラストマー成形品の表面に、非粘着性及
び低摩擦性を付与させるための表面改質方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for surface modification of fluorine-containing elastomer molded articles. More specifically, the present invention relates to a surface modification method for imparting non-adhesion and low friction properties to the surface of a fluorine-containing elastomer molded article.
従来の技術
従来、フッ素ゴムは耐熱性、耐油正、耐溶剤性などのバ
ランスに優れることから、例えば自動車、工業機械、化
学プラントなどの分野において幅広く用いられている。BACKGROUND ART Conventionally, fluororubber has been widely used in fields such as automobiles, industrial machinery, and chemical plants because of its excellent balance of heat resistance, oil resistance, and solvent resistance.
このフッ素ゴムにおいては、特に自動車の吸排気系統、
燃料系統の制御パルプなどに用いられる場合、その表面
が非粘着性であることが要求される。This fluororubber is particularly useful for automobile intake and exhaust systems,
When used as control pulp for fuel systems, the surface is required to be non-adhesive.
ところで、フッ素ゴムは化学的に安定であるため、一般
的に表面改質が困難であるが、これまでに例えばフッ素
ガスや第二級アミンを用いる方法、あるいは液体７ンモ
ニ７中において金属ナトリウムで処理することにより表
面を非粘着性及び低摩擦性にする方法がしられている（
特公昭６１−２４７７４４号公報）。By the way, since fluororubber is chemically stable, it is generally difficult to surface modify it, but so far, methods using fluorine gas or secondary amines, or methods using metallic sodium in liquid 7mmonium have been reported. A method is known to make the surface non-adhesive and low-friction by treating it (
(Special Publication No. 61-247744).
しかしながら、前者の方法においては、成形品の表面が
硬化して、ゴムとしての性質がそこなわれることが多い
し、また、後者の方法においては、危険性が高い液体７
ンモニ７と金属ナトリウムを使用する上に、−ＴＯ〜−
３５℃という超低温雰囲気で作業する必要があるために
、装置及び取扱いの点で実用的でない。However, in the former method, the surface of the molded product often hardens and its properties as a rubber are impaired, and in the latter method, the highly dangerous liquid 7
In addition to using nitrogen 7 and metallic sodium, -TO~-
Since it is necessary to work in an ultra-low temperature atmosphere of 35° C., it is not practical in terms of equipment and handling.
一方、物理的表面処理方法として、例えばフッ素樹脂コ
ーティング方法、高エネルギーによるエツチング方法、
デポジット方法などが知られている。On the other hand, physical surface treatment methods include, for example, fluororesin coating methods, high energy etching methods,
Deposit methods are known.
しかしながら、これらの方法においては、いずれも表面
の非粘着化や低摩擦化については十分に満足しうるむの
ではなく、その上処理コストの上昇を免れない。さらに
、フッ素ゴム中の含まれる低分子量成分や低揮発成分な
どをＦルエンのような溶媒で抽出する方法も知られてい
るが、このような方法では、表面の非粘着化や低摩擦化
は十分に、達成されない。However, in none of these methods can the surface be made non-adhesive or low in friction, and furthermore, processing costs inevitably increase. Furthermore, a method is known in which low molecular weight components and low volatile components contained in fluororubber are extracted using a solvent such as F-luene, but such methods cannot make the surface non-stick or low friction. Enough is not achieved.
発明が解決しようとする問題点
本発明は、このような従来のフッ素ゴムの表面処理方法
が有する欠点を完服し、極めて簡単な操作により、含フ
ッ素エラストマー加硫成形品の表面に、エラストマーと
しての物性をなんらそこなうことな（、非粘着性及び低
摩擦性を付与するための工業的な表面改質方法を提供す
ることを目的としてなされたものである。Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional fluororubber surface treatment methods, and can coat the surface of a fluorine-containing elastomer vulcanized product as an elastomer by an extremely simple operation. The purpose of this work was to provide an industrial surface modification method for imparting non-adhesive properties and low friction properties without impairing the physical properties of the material.
問題点を解決するための手段
本発明者は簡単な手段で含フッ素エラストマーの表面改
質を行いうる方法を開発するために鋭意研究を重ねた結
果、ポリヒドロキシ化合物を含フッ素エラストマー加硫
成形品の表面に含浸させ、二次加硫することにより、そ
の目的を達成しうろことを見い出し、この知見に基づい
て本発明を完成するに至った。Means for Solving the Problems The present inventor has conducted intensive research to develop a method for surface modification of fluorine-containing elastomers using simple means, and as a result, has developed a polyhydroxy compound into a fluorine-containing elastomer vulcanized molded product. The inventors have found that the objective can be achieved by impregnating the surface of the resin and subjecting it to secondary vulcanization, and based on this knowledge, the present invention has been completed.
すなわち、本発明は、含フッ素エラストマーの加硫成形
品の表面に、ポリヒドロキシ化合物の存在下で二次加硫
することを特像とする含フッ素エラストマー成形品の表
面改質方法を提供するものである。That is, the present invention provides a method for surface modification of a fluorine-containing elastomer molded article, which features secondary vulcanization of the surface of the fluorine-containing elastomer molded article in the presence of a polyhydroxy compound. It is.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法が適用される含フッ素エラストマーの加硫成
形品は、例えばフッ化ビニリデン−六フッ化プロピレン
共重合体、７）化ビニリデンー六７フ化プロピレン−四
フッ化エチレン三元共重合体及びこれらの臭素又はヨウ
素含有共重合体、あるいはフッ素系エーテル共重合体な
どのポリヒドロキシ加硫可能な含フッ素エラストマーか
ら成る加硫成形品である。Vulcanized molded products of fluorine-containing elastomers to which the method of the present invention is applied include, for example, vinylidene fluoride-propylene hexafluoride copolymer, vinylidene fluoride-propylene hexafluoride-ethylene tetrafluoride terpolymer, and It is a vulcanized molded article made of a polyhydroxy vulcanizable fluorine-containing elastomer such as these bromine- or iodine-containing copolymers or fluorine-based ether copolymers.
前記含フッ素エラストマーの中で、特にフッ素含量が６
３〜７１重１％、極限粘度が８０〜５００ｚＮ／ｇ、分
子量５万以下のポリマー成分含量が１５重１％以下のも
のが好適である。Among the fluorine-containing elastomers, those with a fluorine content of 6
Preferably, it has a polymer component content of 3-71% by weight, an intrinsic viscosity of 80-500zN/g, and a molecular weight of 50,000 or less and a content of 15% by weight or less.
また、該加硫成形品は、前記含フッ素エラストマーに、
例えば酸化マグネシウムなどの二価の金属酸化物、水酸
化カルシウムなどの二価の金属水酸化物、カーボンブラ
ック、さらには加硫剤や加硫促進剤などを配合して、加
硫成形したものである。Further, the vulcanized molded product includes the fluorine-containing elastomer,
For example, it is vulcanized and molded by blending divalent metal oxides such as magnesium oxide, divalent metal hydroxides such as calcium hydroxide, carbon black, and even vulcanizing agents and vulcanization accelerators. be.
本発明方法においては、加硫剤としてポリヒドロキシ化
合物が用いられる。このポリヒドロキシ化合物としては
、例えばビスフェノールＡ、ハイドロ斗ノン、ペンタエ
リスリトール、ビスフェノールＡＦなどが挙げられるが
、これらの中で特にビス７エ７−ルＡＦが好ましい。In the method of the present invention, a polyhydroxy compound is used as a vulcanizing agent. Examples of the polyhydroxy compound include bisphenol A, hydrodonone, pentaerythritol, and bisphenol AF, and among these, bis7er7-el AF is particularly preferred.
本実発明方法においては、これらのポリヒドロキシ化合
物を適当な有機溶媒に溶解して表面処理液を調製し、こ
の溶液を、含フッ素エラストマーの加硫成形品の表面に
含浸させ、二次加硫することによって該表面を改質する
。該有機溶媒については特に制限はないが、含フッ素エ
ラストマーを膨潤させるもの、例えばアセトン、メチル
エチルケトン、アセトン−メタ／−ル混合系などが好適
である。In the method of the present invention, a surface treatment solution is prepared by dissolving these polyhydroxy compounds in an appropriate organic solvent, and this solution is impregnated onto the surface of a vulcanized molded product of fluorine-containing elastomer, and the secondary vulcanization is performed. The surface is modified by The organic solvent is not particularly limited, but those that swell the fluorine-containing elastomer, such as acetone, methyl ethyl ketone, acetone-metal mixture systems, etc., are suitable.
本発明方法においては、前記のポリヒドロキシ化合物を
含有する表面処理液に、所望に応じ加硫促進剤を溶解さ
せてもよい。この加硫促進剤としては、例えばオルガノ
四級アンモニウムハライド、オル〃ノホスホニウムハラ
イド、ビス〔オル〃７ホスフイン〕イミニウムハライド
などが用いられる。それぞれの代表的なものとしては、
８−ベンジル−１，８−ジアザ−ビシクロ（５，４，０
）−７−ウンゾセニウムクロリド、ペンシルトリフェニ
ルホスホニウムクロリド、ビス〔ベンジルジフェニルホ
スフィンコイミニウムクロリドが挙げられる。In the method of the present invention, a vulcanization accelerator may be dissolved in the surface treatment liquid containing the polyhydroxy compound as desired. Examples of the vulcanization accelerator used include organo-quaternary ammonium halide, ornophosphonium halide, and bis[or-7phosphine]iminium halide. Representative examples of each are:
8-benzyl-1,8-diaza-bicyclo(5,4,0
)-7-unzocenium chloride, pencyltriphenylphosphonium chloride, and bis[benzyldiphenylphosphine coiminium chloride.
本発明方法においては、含フッ素エラストマーの加硫成
形品の表面に、前記の表面処理液を含浸させるには、通
常浸せき法が用いられる０表面処理液の濃度や、浸せき
の温度、時間については特に制限はないが、該表面にお
ける処理液の含浸量が多すぎると、成形品の硬度が大幅
に上昇し、ゴム弾性が低下するので、高温度の表面処理
液に短時間浸せきして、該処理液を膨潤含浸させ、二次
加硫することにより、表面のみの架橋密度を大きくする
ことが望ましい。この方法によって、該含フッ素エラス
トマーの加硫成形品は、硬度の上昇が小さくてゴム弾性
がそこなわれることな（、表面に非粘着性と低摩擦性が
付与される上に、引張時のクラックの発生もなく、かつ
破断伸度の低下も抑えることができる。In the method of the present invention, a dipping method is usually used to impregnate the surface of a vulcanized product of fluorine-containing elastomer with the surface treatment liquid.The concentration of the surface treatment liquid, the temperature and time of dipping are Although there is no particular limit, if the amount of treatment liquid impregnated on the surface is too large, the hardness of the molded product will significantly increase and the rubber elasticity will decrease. It is desirable to increase the crosslinking density only on the surface by swelling and impregnating with a treatment liquid and performing secondary vulcanization. By this method, the vulcanized molded product of the fluorine-containing elastomer has a small increase in hardness and its rubber elasticity is not impaired (it also has non-adhesive and low friction properties on the surface, and also No cracks occur, and a decrease in elongation at break can be suppressed.
また、溶媒の膨潤性の程度によって、適正な表面処理液
濃度、浸せき温度、浸せき時間は左右されるが、通常表
面処理液中の加硫剤の含有量は１〜５０重量％、加硫促
進剤の含有量は０．３〜２０重１％の範囲で選ばれる。In addition, the appropriate surface treatment solution concentration, immersion temperature, and immersion time depend on the degree of swelling of the solvent, but the content of the vulcanizing agent in the surface treatment solution is usually 1 to 50% by weight to promote vulcanization. The content of the agent is selected within the range of 0.3 to 20 1% by weight.
処理温度は０〜１００℃の範囲が好ましく、処理時間は
２〜１２０分聞程度が好適である。The processing temperature is preferably in the range of 0 to 100°C, and the processing time is preferably about 2 to 120 minutes.
このようにして、含フッ素エラストマーの加硫成形品の
゛表面に処理液を含浸させたのち、乾燥後、二次加硫さ
れる。二次加硫の温度、時間については特に制限はない
が一次加硫成形時よりも、高温かつ長時間を要し、二次
加硫温度としては、１８０〜２７０℃の範囲が好ましい
。In this manner, the surface of the vulcanized molded product of fluorine-containing elastomer is impregnated with the treatment liquid, and after drying, it is subjected to secondary vulcanization. There are no particular restrictions on the temperature and time of secondary vulcanization, but it requires a higher temperature and longer time than during primary vulcanization, and the secondary vulcanization temperature is preferably in the range of 180 to 270°C.
発明の効果
本発明方法によって、含フッ素エラストマーの加硫成形
品の表面に、エラストマーとしての物性をそこなうこと
なく、非粘着性及び低摩擦性を付与することができる。Effects of the Invention By the method of the present invention, non-adhesive properties and low friction properties can be imparted to the surface of a vulcanized molded product of a fluorine-containing elastomer without impairing the physical properties of the elastomer.
このようにして表面が改質された含フッ素エラストマー
の加硫成形品は、例えば非粘着性や低摩擦性が要求され
る制御バルブ、オイルシール、グイヤ７ラム、０−リン
グなどに好適に用いられる。Vulcanized molded products of fluorine-containing elastomers whose surfaces have been modified in this way are suitable for use in, for example, control valves, oil seals, Guya 7 rams, O-rings, etc. that require non-stick properties and low friction properties. It will be done.
実施例
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
なお、粘着力は次の方法に従って測定した。Note that the adhesive strength was measured according to the following method.
すなわち、ゴムシート（３５Ｘ３５Ｘ２ｍｍ）を平滑な
台の上に耐熱性の両性テープで貼り、その上に錘り受は
部及び吊り兵を備えた半調（ＪＩＳ Ｓ−４５０）製の
平面リングをゴムシートと接触するように置＜（なお、
リングのサイズは外径２５肩肩、内径１９１１１であり
、ゴムシートと接触する面は＃ １０００研摩紙で研摩
しである）０次いで、リングのｆ！り受は部にゴムシー
トへの全荷重が６０９ｙ／ｃｉ＋”になるように錘りを
乗せる。その全体を１２０℃のオープン中に入れて２０
時間放置後、取り出して約４時開放冷する。２３℃まで
温度が下がったところで錘りをはずし、ゴムシートにリ
ングが粘着状態で上記吊り兵を利用したロードセルを含
む引張試験機に取付け、５０ ｘｉ／ｗｉｎの引張り速
度で引張り粘着力を測定する。That is, a rubber sheet (35 x 35 x 2 mm) is pasted on a smooth table with heat-resistant amphoteric tape, and a flat ring made of half-tone (JIS S-450) with a weight holder and a hanger is placed on top of the rubber sheet. Place it so that it is in contact with the sheet.
The ring has an outer diameter of 25mm and an inner diameter of 19111mm, and the surface that contacts the rubber sheet is polished with #1000 abrasive paper. Place a weight on the holder so that the total load on the rubber sheet is 609y/ci+''.
After leaving it for a while, take it out and let it cool in the open for about 4 hours. When the temperature has fallen to 23°C, remove the weight, attach the ring to the rubber sheet in a state of adhesion to a tensile testing machine that includes a load cell using the above suspension, and measure the tensile adhesive force at a tensile rate of 50 xi/win. .
実施例１〜５
各成分を別表に示す配合割合で用いて、６インチロール
で混練したのち、熱プレスを用いて、１７７℃、１０分
間−次加硫を行い、９０ Ｘ １６０ Ｘ ２ｚｍのシ
ートを作成した。Examples 1 to 5 Each component was used in the proportion shown in the attached table, and after kneading with a 6-inch roll, post-vulcanization was performed at 177°C for 10 minutes using a hot press to form a sheet of 90 x 160 x 2 zm. It was created.
一方、ビスフェノールＡＦ又はこれと加硫促進剤とを含
有するアセトン溶液から成る表面処理液を調製し、この
液中に前記の加硫シートを該表に示す条件で浸せきした
のち、−夜風乾し、さらに１２０℃で３０分間乾燥した
。On the other hand, a surface treatment solution consisting of an acetone solution containing bisphenol AF or bisphenol AF and a vulcanization accelerator was prepared, and the vulcanized sheet was immersed in this solution under the conditions shown in the table, and then air-dried at night. , and further dried at 120° C. for 30 minutes.
次に、このものをオープン中において、２３２℃で２４
時間保持して二次加硫を行い、粘着力を求めた。その結
果を該表に示す。Next, this product was opened at 232℃ for 24 hours.
Secondary vulcanization was performed by holding for a certain period of time, and the adhesive strength was determined. The results are shown in the table.
なお、ポリマーＡにおける分子量５万以下のポリマー成
分含量Ｍ、は、次に示す条件に従って分子量分布を測定
して求めた。The content M of polymer components having a molecular weight of 50,000 or less in Polymer A was determined by measuring the molecular weight distribution according to the following conditions.
液体クロマトグラ７：ＬＣ−３Ａ型（島津製作所（株）
製
カ ラ ム：ＫＦ−８０８（２本）＋ＫＦ−８００Ｆ（
プレカラム）（昭和電工（株）製）
検 出 器：ＥＲＣ−７５１０Ｓ（エルマ光学（株）製
）インチグレーターニア０００Ａ（システムインスツル
メンツ社製）
展開溶媒：テシラヒドロ７ラン
濃 度二０．１重量％
温 度：３５℃
分子量検量線用標準ポリマー：
単分散ポリスチレン各種（東洋曹
達（株）製）（Ｍ ／Ｈ−１，２（ｆｆ１ａｘ＞）比較
例１．２
別表に示す配合組成を用い、かつ表面処理しないこと以
外は、実施例１〜５と同様な操作を行った。その結果を
該表に示す。Liquid chromatograph 7: LC-3A type (Shimadzu Corporation)
Manufactured columns: KF-808 (2 pieces) + KF-800F (
Precolumn) (manufactured by Showa Denko K.K.) Detector: ERC-7510S (manufactured by Elma Optical Co., Ltd.) Inch Graternia 000A (manufactured by System Instruments) Developing solvent: Tesilahydro 7 run concentration 20.1% by weight Temperature Temperature: 35°C Standard polymer for molecular weight calibration curve: Various types of monodispersed polystyrene (manufactured by Toyo Soda Co., Ltd.) (M/H-1,2 (ff1ax>) Comparative Example 1.2 Using the formulation shown in the attached table, and The same operations as in Examples 1 to 5 were performed except that no treatment was performed.The results are shown in the table.
実施例と比較例の結果から、本発明の方法による非粘着
性、低摩擦性の付与は単なる硬度上昇によるものでない
ことが明らかであり、その効果は著しい。From the results of Examples and Comparative Examples, it is clear that the imparting of non-adhesion and low friction properties by the method of the present invention is not simply due to an increase in hardness, and the effect is remarkable.
手続補正書
昭和６２年８月３日
１、事件の表示
昭和６２年特許願第１２５０３０号
２、発明の名称
含フッ素エラストマー成形品の表面改質方法３、補正を
する者
事件との関係 特許出願人
大阪府大阪市北区堂島浜１丁目２番６号（００３）旭化
成工業株式会社
代表者世古真臣
４、代理人
東京都港区新橋２丁目２番２号川志満・邦信ビル８階５
、補正命令の日付 自 発
６、補正により増加する発明の数 ０
７、補正の対象 明細書の特許請求の範囲の欄８、
補正の内容
（１）特許請求の範囲を別紙のとおり訂正します。Procedural amendment dated August 3, 1988 1. Indication of the case Patent Application No. 125030 of 1988 2. Name of the invention Method for surface modification of fluorine-containing elastomer molded products 3. Person making the amendment Relationship with the case Patent application Person: 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture (003) Asahi Kasei Industries Co., Ltd. Representative: Masaomi Seko 4, Agent: 5-5, 8th floor, Kawashima Kunishin Building, 2-2-2 Shinbashi, Minato-ku, Tokyo
, Date of amendment order: 6, Number of inventions increased by amendment: 0 7, Subject of amendment: Scope of claims in the specification, column 8,
Contents of amendment (1) The scope of patent claims will be corrected as shown in the attached sheet.
（２）明細書第２ページ第２行の「耐油正」を「耐油性
」に訂正します。(2) Correct "Oil resistance" in the second line of the second page of the specification to "Oil resistance."
（３）同第２ページ第１４行の「特公昭６１−」を「待
閏昭６１−」に訂正します。(3) On the 2nd page, line 14, "Tokuko Sho 61-" is corrected to "Taiban Sho 61-".
（４）同第６ページ第５〜７行の「ポリヒドロキシル化
合物〜二次加硫する」を、「いったん加硫した含フッ素
エラストマー成形品の表面にポリヒドロキシル化合物を
含浸させ、再度加硫する」に訂正します。(4) "Polyhydroxyl compound - secondary vulcanization" on page 6, lines 5 to 7 of the same page was changed to "impregnating the surface of the fluorine-containing elastomer molded product once vulcanized with a polyhydroxyl compound and vulcanizing it again. ” will be corrected.
（５）同第４ページ第１０〜１２行の［含フッ素エラス
トマーの・・・二次加硫する］を［含フッ素エラストマ
ー成形品をいったん加硫処理したのち、この処理物の表
面にポリヒドロキシル化合物を含浸させ、再度加硫する
」に訂正します。(5) On page 4, lines 10 to 12, [secondary vulcanization of the fluorine-containing elastomer] is changed to [After the fluorine-containing elastomer molded product is once vulcanized, polyhydroxyl is added to the surface of the treated product. Impregnated with compound and vulcanized again.''
（６）同第４ページ下より４行の「ペンタエリスリトー
ル、」を削除します。(6) Delete 4 lines of "Pentaerythritol," from the bottom of the 4th page.
（７）同第６ページ第３行の「二次加硫」を「再度加硫
」に訂正します。(7) "Secondary vulcanization" in the third line of page 6 will be corrected to "re-vulcanization."
（８）同第６ページ第１０行の「所望に応じ」の次に［
非粘着性をさらに向上させるための」を加入します。(8) On page 6, line 10, next to “as requested” [
Added "to further improve non-stick properties."
（９）同第６ページ下より２行の「・・・が挙げられる
。」の次に以下の文章を加入します。(9) Add the following sentence next to the two lines from the bottom of page 6, "The following are mentioned."
「このほか、加硫促進剤の効果をよりいっそう高めるた
めの加硫促進活性剤として、ジメチルスルホン、ｐ、ｐ
′−ゾクロロシフェニルスルホンのようなスルホン類や
、ジメチルスルホキシド、ジエチルスルホキシドのよう
なスルホキシド類を加えることらで軽る。」
（１０）同第７ページ第６行の「高温度」を「高濃度」
に訂正します。"In addition, dimethyl sulfone, p, p
It can be reduced by adding sulfones such as '-zochlorocyphenylsulfone and sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide. ” (10) “High temperature” in line 6 of page 7 of the same document is changed to “high concentration.”
I will correct it.
（１１）同第７ベーゾ第７行の「二次」を「再度」に訂
正します。(11) “Secondary” in line 7 of the 7th beso will be corrected to “again”.
（１２） ｆｉ１８ページ第２〜７行の「このように
して、・・・好ましい、」を以下のとお９訂正します。(12) The following 9 corrections have been made to "In this way...it is preferable," in lines 2 to 7 of page 18 of fi.
［このようにして、いったん加硫処理した含フッ素エラ
ストマー成形品の表面に、ポリヒドロキシル化合物を含
有する処理液を含浸させ、乾燥したのち、再度加硫処理
を行う、この際の温度、時間については加硫が達成され
る限り特に制限はないが、通常は最初の加硫の場合より
も高温でかつ長時間行われる。この加硫温度としては１
８０〜２７０℃の範囲が好適である。」
（１３）同第１２ページの表中、下から２番目の「二次
加硫後のＨｓＪの横の実施例５の数値「８３」を「８１
ｊに、また比較例２の数値「８１」を「７８」にそれぞ
れ訂正します。[In this way, the surface of the fluorine-containing elastomer molded product once vulcanized is impregnated with a treatment liquid containing a polyhydroxyl compound, dried, and then vulcanized again. Regarding the temperature and time at this time. The vulcanization is not particularly limited as long as vulcanization is achieved, but is usually carried out at a higher temperature and for a longer time than the initial vulcanization. This vulcanization temperature is 1
A temperature range of 80 to 270°C is suitable. (13) In the table on page 12, the second value from the bottom next to "HsJ after secondary vulcanization" in Example 5 was changed from "83" to "81".
j, and the numerical value "81" in Comparative Example 2 to "78".
（１４）同第１２ページの表の最下欄の「剥離強さ」を
「粘着力」に訂正します。(14) "Peel strength" in the bottom column of the table on page 12 will be corrected to "adhesive strength."
特許請求の範囲
１ 含フッ素エラストマー成形品をいったん処理したの
ち、この処理物の表面にポリヒドロキシ化合物ｅｒａｓ
−ｅユＪｆｉ−加硫することを特徴とする含フッ素エラ
ストマー成形品の表面改質方法。Claim 1: After a fluorine-containing elastomer molded article is once treated, a polyhydroxy compound ERAS is applied to the surface of the treated article.
-eyuJfi- A method for surface modification of a fluorine-containing elastomer molded article, which comprises vulcanization.
２ 含フッ素エラストマーが、フッ素含量６３〜７１重
１％、極限粘度８０〜５００ｘ１／ｇ及び分子量５万以
下のポリマー成分含量１５重量％以下のものである特許
請求の範囲第１項記載の方法。2. The method according to claim 1, wherein the fluorine-containing elastomer has a fluorine content of 63 to 71% by weight, an intrinsic viscosity of 80 to 500x1/g, and a polymer component content of 15% by weight or less with a molecular weight of 50,000 or less.
手続補正書
昭和６２年８月１３日
特許庁長官 小 川 邦 夫 殿
１、事件の表示
昭和６２年特許顧第１２５０３０号
２、発明の名称
含フッ素エラストマー成形品の表面改質方法３、補正を
する者
事件との関係 特許出願人
大阪府大阪市北区堂島浜１丁目２番６号（００３）旭化
成工業株式会社
代表者世古真臣
４、代理人
６、補正により増加する発明の数 ０
７、補正の対象 明細書の特許請求の範囲の欄及び発
明の詳細な説明の欄
８、補正の内容
昭和６２年８月３日付手続補正書により訂正した個所を
全て訂正前の状態に戻したのち、改めて以下の補正を行
います。Procedural amendment August 13, 1988 Kunio Ogawa, Commissioner of the Patent Office1, Indication of the case Patent Office No. 125030 of 19882, Name of the invention Method for surface modification of fluorine-containing elastomer molded products 3, Amendment Patent applicant: 1-2-6 Dojimahama, Kita-ku, Osaka, Osaka Prefecture (003) Asahi Kasei Industries, Ltd. Representative: Masami Seko 4, Agent: 6 Number of inventions increased by amendment 0 7, Amendment Scope of Claims column of the specification, Detailed Description of the Invention column 8, Contents of the amendment After restoring all the parts corrected by the procedural amendment dated August 3, 1985 to the state before the correction, Perform the following corrections.
（１）特許請求の範囲を別紙のとおり訂正します。(1) The scope of patent claims will be amended as shown in the attached sheet.
（２）明細書第２ページ第２行の「耐油正」を、「耐油
性」に訂正します。(2) "Oil resistance" in the second line of the second page of the specification will be corrected to "oil resistance."
（３）同第２ページ第１４行の「特公昭６１−」を、「
特開昭６１−」に訂正します。(3) Change “Tokuko Sho 61-” on the 14th line of the second page to “
Corrected to ``JP-A-61-''.
（４）同第４ページ第６〜７行の「二次加硫する」を、
「再度加硫する」に訂正します。(4) "Secondary vulcanization" on page 4, lines 6-7,
Corrected to "re-vulcanize".
（５）同第４ページ第１１〜１２行の「ポリヒドロキシ
化合物の存在下で二次加硫する」を、「ポリヒドロキシ
ル化合物を含浸させ、再度加硫する」に訂正します。(5) On page 4, lines 11-12, "secondary vulcanization in the presence of a polyhydroxyl compound" is corrected to "impregnate with a polyhydroxyl compound and vulcanize again."
（６）同第５ページ下よＹ）４行の「ペンタエリスリト
ール、」を削除します。(6) At the bottom of page 5, delete the 4th line "Pentaerythritol."
（７）同第６ページ第３行の「二次加硫」を、「再度加
硫」に訂正します。(7) "Secondary vulcanization" in the third line of page 6 will be corrected to "re-vulcanization."
（８）同ｐＩＩＪ６ベーノ＃１１０行の「所望に応じ」
の次に「非粘着性をさらに向上させるための」を加入し
ます。(8) “As desired” in pIIJ6 Beno #110 line
Next, add ``To further improve non-adhesiveness.''
（９）同第６ページ下より２行の［・・・が挙げられる
。」の次に以下の文章を加入します。(9) Two lines from the bottom of the 6th page include [...]. Add the following text after ``.
［このほか、加硫促進剤の効果をよりいっそう高めるた
めの加硫促進活性剤として、ジメチルスルホン、ρ、ｐ
’−ジクロロジフェニルスルホンのよウナスルホン類や
、ジメチルスルホキシド、ジエチルスルホ斗シトのよう
なスルホキシド類を加えることもできる。」
（１０）同第７ページ＠６行の「高温度」を、「高濃度
」に訂正します。[In addition, dimethyl sulfone, ρ, p
It is also possible to add una sulfones such as '-dichlorodiphenyl sulfone, and sulfoxides such as dimethyl sulfoxide and diethyl sulfonate. ” (10) “High temperature” on page 7, line 6 will be corrected to “high concentration.”
（１１）同第７ページ第７行の「二次」を、「再度」に
訂正します。(11) “Secondary” in line 7 of page 7 will be corrected to “again.”
（１２）同第８ページ第４〜７行の「二次加硫される。(12) On page 8, lines 4 to 7, “Secondary vulcanization is performed.
・・・好ましい。」を以下のとおり訂正します。···preferable. ” is corrected as follows.
［再度加硫処理を行う、この際の温度、時間については
加硫が達成される限り特に制限はないが、通常は最初の
加硫の場合よりも高温でかつ長時間行われる。この加硫
温度としては１８０〜２７０℃の範囲が好適である。」
（１３）同第１２ページの表中の項目の表示第９番目「
−次加硫」を「最初の加硫」に、下から３番目の「二次
加硫」を「再度加硫」に、下から２番目の［二次加硫後
のＨｓＪを［再度加硫後のＨｓＪに、また、「再度加硫
後のＨｓＪ（補正後）の欄の実施例５の数値「８３」を
「８１」に、主た比較例２の数値「８１」を「７８」に
それぞれ訂正します。[The temperature and time of performing the vulcanization treatment again are not particularly limited as long as vulcanization is achieved, but the vulcanization is usually performed at a higher temperature and for a longer time than in the case of the first vulcanization. The vulcanization temperature is preferably in the range of 180 to 270°C. ” (13) 9th item in the table on page 12: “
- Next vulcanization" to "First vulcanization", third from the bottom "Secondary vulcanization" to "Re-vulcanization", second from the bottom "HsJ after secondary vulcanization to [Re-vulcanization] For HsJ after sulfurization, the value ``83'' of Example 5 in the column ``HsJ after re-vulcanization (after correction)'' was changed to ``81'', and the value ``81'' of Main Comparative Example 2 was changed to ``78''. I will correct each.
（１４）同第１２ページの表の最下槽の「剥離強さ」を
、「粘着力」に訂正します。(14) "Peel strength" in the bottom tank of the table on page 12 will be corrected to "adhesion strength."
特許請求の範囲
１ 含フッ素エラストマーの加硫成形品の表面片ボリヒ
Ｙａえシ化合物１１」【灸竺ユ」１庫、加硫することを
特徴とする含フッ素エラストマー成形品の表面改質方法
。Claim 1: A method for surface modification of a fluorine-containing elastomer molded article, which comprises vulcanizing a surface piece of a fluorine-containing elastomer vulcanized molded article.
２ 含フッ素エラストマーが、フッ素含量６３〜７１重
１％、極限粘度８０〜５０（ｍ２／９及び分子量５万以
下のポリマー成分含量１５重量％以下のものである特許
請求の範囲第１項記載の方法。2. The fluorine-containing elastomer has a fluorine content of 63 to 71% by weight, an intrinsic viscosity of 80 to 50 (m2/9), and a polymer component content of 15% by weight or less with a molecular weight of 50,000 or less. Method.
Claims (1)
ヒドロキシ化合物の存在下で二次加硫することを特徴と
する含フッ素エラストマー成形品の表面改質方法。 ２ 含フッ素エラストマーが、フッ素含量６３〜７１重
量％、極限粘度８０〜５００ｍｌ／ｇ及び分子量５万以
下のポリマー成分含量１５重量％以下のものである特許
請求の範囲第１項記載の方法。[Scope of Claims] 1. A method for surface modification of a fluorine-containing elastomer molded article, which comprises subjecting the surface of the fluorine-containing elastomer molded article to secondary vulcanization in the presence of a polyhydroxy compound. 2. The method according to claim 1, wherein the fluorine-containing elastomer has a fluorine content of 63 to 71% by weight, an intrinsic viscosity of 80 to 500ml/g, and a polymer component content of 15% by weight or less with a molecular weight of 50,000 or less.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62125030A JPS63291930A (en) | 1987-05-23 | 1987-05-23 | Method for modifying surface of molded fluorine-containing elastomer product |
| EP88107173A EP0292747B1 (en) | 1987-05-23 | 1988-05-04 | A shaped article of a crosslinked elastomer |
| DE3886818T DE3886818T2 (en) | 1987-05-23 | 1988-05-04 | Object molded from a cross-linked elastomer. |
| US07/191,063 US4981912A (en) | 1987-05-23 | 1988-05-06 | Shaped article of a crosslinked elastomer |
| CA000567375A CA1325507C (en) | 1987-05-23 | 1988-05-20 | Shaped article of a crosslinked elastomer |
| KR1019880006024A KR910003958B1 (en) | 1987-05-23 | 1988-05-21 | A shaped aticle of a crosslinked elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62125030A JPS63291930A (en) | 1987-05-23 | 1987-05-23 | Method for modifying surface of molded fluorine-containing elastomer product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291930A true JPS63291930A (en) | 1988-11-29 |
| JPH0437094B2 JPH0437094B2 (en) | 1992-06-18 |
Family
ID=14900109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62125030A Granted JPS63291930A (en) | 1987-05-23 | 1987-05-23 | Method for modifying surface of molded fluorine-containing elastomer product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63291930A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04236232A (en) * | 1991-01-17 | 1992-08-25 | Asahi Chem Ind Co Ltd | Production of varcanized formed body |
| WO2007080681A1 (en) * | 2006-01-11 | 2007-07-19 | Nok Corporation | Process for producing crosslinked fluororubber |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
| JP2021507074A (en) * | 2017-12-22 | 2021-02-22 | スリーエム イノベイティブ プロパティズ カンパニー | Peroxide-cured halogenated elastomer with a silicon-containing surface layer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6630513B2 (en) * | 2015-08-05 | 2020-01-15 | 西川ゴム工業株式会社 | Manufacturing method of vibration damping rubber sheet |
-
1987
- 1987-05-23 JP JP62125030A patent/JPS63291930A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04236232A (en) * | 1991-01-17 | 1992-08-25 | Asahi Chem Ind Co Ltd | Production of varcanized formed body |
| WO2007080681A1 (en) * | 2006-01-11 | 2007-07-19 | Nok Corporation | Process for producing crosslinked fluororubber |
| JP2007186554A (en) * | 2006-01-11 | 2007-07-26 | Nok Corp | Method for producing crosslinked fluororubber |
| KR101001833B1 (en) | 2006-01-11 | 2010-12-15 | 에누오케 가부시키가이샤 | Process for producing crosslinked fluororubber |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
| JP2021507074A (en) * | 2017-12-22 | 2021-02-22 | スリーエム イノベイティブ プロパティズ カンパニー | Peroxide-cured halogenated elastomer with a silicon-containing surface layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0437094B2 (en) | 1992-06-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |