JP2015137304A - Surface treatment liquid for rubber seal and surface modification method of rubber seal using the surface treatment liquid - Google Patents
Surface treatment liquid for rubber seal and surface modification method of rubber seal using the surface treatment liquid Download PDFInfo
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- JP2015137304A JP2015137304A JP2014009355A JP2014009355A JP2015137304A JP 2015137304 A JP2015137304 A JP 2015137304A JP 2014009355 A JP2014009355 A JP 2014009355A JP 2014009355 A JP2014009355 A JP 2014009355A JP 2015137304 A JP2015137304 A JP 2015137304A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 88
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 238000004381 surface treatment Methods 0.000 title claims abstract description 39
- 238000002715 modification method Methods 0.000 title abstract description 4
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 19
- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims description 33
- 229920000459 Nitrile rubber Polymers 0.000 claims description 21
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 17
- 150000002576 ketones Chemical class 0.000 claims description 16
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical group CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 15
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 11
- 229950009390 symclosene Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- -1 tert-heptyl Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 239000005456 alcohol based solvent Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000003759 ester based solvent Substances 0.000 abstract description 2
- 239000005453 ketone based solvent Substances 0.000 abstract description 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 4
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Sealing Devices (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、ゴムシールの伸張性を低下させることなく、ゴムシールの表面に低摩擦性を付与し、かつ、保管時のゴムシール同士の粘着防止を図るための技術に関する。 The present invention relates to a technique for imparting low friction to the surface of a rubber seal without reducing the extensibility of the rubber seal and preventing adhesion between the rubber seals during storage.
従来からトリクロロイソシアヌル酸を使用してゴムや樹脂の表面処理を行うことが知られている。例えば、特許文献１、２にはトリクロロイソシアヌル酸によってゴム表面の摩擦係数低減と耐オゾン性の改良が図られることが開示されている。また、特許文献２にはトリクロロイソシアヌル酸を水に溶解させた処理液はトリクロロイソシアヌル酸を有機溶媒に溶解させた処理液に比べてゴムに発生するシワを防止できる点で有利であることが謳われている。 Conventionally, it is known to perform surface treatment of rubber or resin using trichloroisocyanuric acid. For example, Patent Documents 1 and 2 disclose that trichloroisocyanuric acid can reduce the friction coefficient of the rubber surface and improve ozone resistance. Patent Document 2 discloses that a treatment liquid in which trichloroisocyanuric acid is dissolved in water is advantageous in that wrinkles generated in rubber can be prevented as compared with a treatment liquid in which trichloroisocyanuric acid is dissolved in an organic solvent. It has been broken.
ところで、電車などのドアの開閉駆動に用いられる空気圧シリンダ、電磁弁、または、スプール弁などにおける摺動部分、すなわち、回転や往復運動する部材（ピストン、スプール等）とこれに対面する部材（シリンダ、スリーブ等）間には、その摺動性を損なうことなく、これらの間に流れる流体を密封するために、パッキンなどのシールが装着される。このような摺動部分に適用される、所謂、摺動部用シールにおいては、運動部の摺動性を損なうことなく、運動部を作動させる作動液体または作動気体を密封することが必要となるため、表面の摩擦係数が小さいことが要求される。この種のシールとしては、例えば、コスト、耐油性等の観点から、ニトリルゴム（ＮＢＲ）が多く使用されているが、ニトリルゴムは摩擦係数が高い。このため、ニトリルゴムからなるシールの表面を上述の従来の処理液で処理をしたところ、処理液がシールの内部まで浸透して、シールの内部まで処理されてしまい、その結果、シールを伸張するとシールの表面に亀裂が発生し、シール性能が低下してしまうことが分かった。また、工業的に大量生産された、主成分がゴムからなるシールは、装置や機器に実際に装着する作業を行うまでは一括して保管されるために、保管されている間にシール同士が付着し、装置や機器に装着する前に付着したシール同士を分離する作業が必要になる。このため、シールが装着される装置や機器の製造効率を低下させる原因になっている。 By the way, a sliding part in a pneumatic cylinder, electromagnetic valve, or spool valve used for opening and closing a door of a train or the like, that is, a member that rotates or reciprocates (piston, spool, etc.) and a member that faces this (cylinder) In order to seal the fluid flowing between them without losing their slidability, a seal such as a packing is attached between the sleeves and the like. In a so-called sliding portion seal applied to such a sliding portion, it is necessary to seal the working liquid or working gas that operates the moving portion without impairing the sliding property of the moving portion. Therefore, it is required that the surface friction coefficient is small. As this type of seal, for example, nitrile rubber (NBR) is often used from the viewpoint of cost, oil resistance, etc., but nitrile rubber has a high coefficient of friction. For this reason, when the surface of the seal made of nitrile rubber is treated with the above-described conventional treatment liquid, the treatment liquid penetrates into the inside of the seal and is treated to the inside of the seal. It was found that cracks occurred on the surface of the seal and the sealing performance deteriorated. Also, industrially mass-produced seals consisting mainly of rubber are stored in a lump until they are actually installed on devices and equipment. It is necessary to work to separate the stickers that have adhered and adhered to each other before being attached to an apparatus or device. For this reason, it is the cause of reducing the manufacturing efficiency of the apparatus and apparatus with which a seal | sticker is mounted | worn.
本発明は、上記の事情に鑑みて成されたものであり、その解決しようとする課題は、主成分がゴムからなるシール（以下、単に「ゴムシール」ともいう。）に対して、伸張性を低下させることなく、表面に低摩擦性を付与でき、しかも、保管時のゴムシール同士の付着防止（以下、「防着」とも略称する）効果も付与できる、ゴムシール用表面処理液および該表面処理液を使用したゴムシールの表面改質方法を提供することにある。 The present invention has been made in view of the above-described circumstances, and the problem to be solved is to provide extensibility with respect to a seal whose main component is made of rubber (hereinafter also simply referred to as “rubber seal”). Surface treatment liquid for rubber seal and surface treatment liquid capable of imparting low friction property to the surface without lowering and also providing an effect of preventing adhesion between rubber seals during storage (hereinafter also abbreviated as “anti-adhesion”) It is an object of the present invention to provide a surface modification method for a rubber seal using
本発明者等は、上記の課題を解決するために鋭意研究した結果、第３級アルコール系溶媒と、エステル系溶媒および／またはケトン系溶媒とを含む混合溶媒にトリクロロイソシアヌル酸等の塩素化イソシアヌル酸を配合して得られる処理液は、ゴムシールの内部への浸透が抑制されて、ゴムシールの伸張性を損なうことなく、ゴムシールの表面に低摩擦性と防着性を付与し得ることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have found that a chlorinated isocyanuric acid such as trichloroisocyanuric acid is mixed in a mixed solvent containing a tertiary alcohol solvent and an ester solvent and / or a ketone solvent. The treatment liquid obtained by blending the acid has been found to be able to impart low friction and adhesion to the surface of the rubber seal without impairing the inside of the rubber seal and impairing the extensibility of the rubber seal. The present invention has been completed.
すなわち、本発明は以下の特徴を有する。
［１］ （Ａ）塩素化イソシアヌル酸、（Ｂ）第３級アルコール系溶媒、並びに（Ｃ）エステル系溶媒および／またはケトン系溶媒を含む、ゴムシール用表面処理液。
［２］ （Ａ）塩素化イソシアヌル酸が、トリクロロイソシアヌル酸である、上記［１］記載のゴムシール用表面処理液。
［３］ （Ｂ）第３級アルコール系溶媒が、ｔｅｒｔ−アミルアルコールおよび／またはｔｅｒｔ−ヘプチルアルコールである、上記［１］または［２］記載のゴムシール用表面処理液。
［４］ （Ｂ）第３級アルコール系溶媒と（Ｃ）エステル系溶媒および／またはケトン系溶媒との配合比（（Ｂ）：（Ｃ））が、重量比で５：５〜８：２である、上記［１］〜［３］のいずれか１つに記載のゴムシール用表面処理液。
［５］ （Ａ）塩素化イソシアヌル酸の含有量が、当該処理液全体当たり１〜１０重量％である、上記［１］〜［４］のいずれか１つに記載のゴムシール用表面処理液。
［６］ ゴムシールがニトリルゴム（ＮＢＲ）を含む、上記［１］〜［５］のいずれか１つに記載のゴムシール用表面処理液。
［７］ ゴムシールが摺動部用ゴムシールである、上記［６］記載のゴムシール用表面処理液。
［８］ 上記［１］〜［５］のいずれか１つに記載の表面処理液をゴムシールの表面に付すことを特徴とする、ゴムシールの表面改質方法。
［９］ 表面処理液中にゴムシールを浸漬することを含む、上記［８］記載の方法。
［１０］ 浸漬時間が１〜１０分である上記［９］記載の方法。
That is, the present invention has the following features.
[1] A rubber seal surface treatment liquid comprising (A) chlorinated isocyanuric acid, (B) a tertiary alcohol solvent, and (C) an ester solvent and / or a ketone solvent.
[2] The surface treatment liquid for rubber seals according to the above [1], wherein (A) the chlorinated isocyanuric acid is trichloroisocyanuric acid.
[3] The surface treatment solution for rubber seals according to the above [1] or [2], wherein the (B) tertiary alcohol solvent is tert-amyl alcohol and / or tert-heptyl alcohol.
[4] The blending ratio ((B) :( C)) of (B) tertiary alcohol solvent and (C) ester solvent and / or ketone solvent is 5: 5 to 8: 2 by weight. The surface treatment liquid for rubber seal according to any one of [1] to [3] above.
[5] The surface treatment liquid for rubber seal according to any one of the above [1] to [4], wherein the content of (A) chlorinated isocyanuric acid is 1 to 10% by weight based on the whole treatment liquid.
[6] The surface treatment liquid for rubber seal according to any one of [1] to [5], wherein the rubber seal contains nitrile rubber (NBR).
[7] The surface treatment liquid for a rubber seal according to the above [6], wherein the rubber seal is a rubber seal for a sliding part.
[8] A method for modifying a surface of a rubber seal, wherein the surface treatment liquid according to any one of [1] to [5] is applied to a surface of the rubber seal.
[9] The method according to [8] above, comprising immersing a rubber seal in the surface treatment liquid.
[10] The method according to [9] above, wherein the immersion time is 1 to 10 minutes.
本発明のゴムシール用表面処理液は、ゴムシールに対して、ゴムシールの伸張性を低下させることなく、低摩擦性および防着性を効果的に付与することができる。特にニトリルゴム（ＮＢＲ）のような表面の摩擦係数が高いゴムを含むゴムシールであっても、伸張性を低下させることなく、低摩擦性を付与できる。このため、例えば、本発明の表面処理液により、ニトリルゴム（ＮＢＲ）を含むゴムシールを表面処理することで、ニトリルゴム（ＮＢＲ）が有する優れた耐油性及び機械的特性を活かしつつ、運動部の摺動性を維持し得る摺動部用シールを実現できる。また、本発明のゴムシール用表面処理液にて処理されたゴムシールは優れた防着性を示すため、保管時のゴムシール同士の付着を防止でき、ゴムシールが装着される装置や機器の製造現場において付着したゴムシール同士を分離する作業が不要になるため、装置や機器の製造効率向上に繋がる。 The surface treatment liquid for rubber seal of the present invention can effectively impart low friction and adhesion to the rubber seal without reducing the extensibility of the rubber seal. In particular, even a rubber seal including a rubber having a high surface friction coefficient such as nitrile rubber (NBR) can impart low friction without reducing extensibility. For this reason, for example, surface treatment of the rubber seal containing nitrile rubber (NBR) with the surface treatment liquid of the present invention makes it possible to take advantage of the excellent oil resistance and mechanical properties of nitrile rubber (NBR) and A seal for a sliding portion that can maintain slidability can be realized. In addition, since the rubber seal treated with the surface treatment liquid for rubber seal of the present invention exhibits excellent adhesion, it is possible to prevent the rubber seals from sticking to each other during storage. Since the operation | work which isolate | separated the rubber seals which became it becomes unnecessary, it leads to the manufacturing efficiency improvement of an apparatus or an apparatus.
以下、本発明をその好適な実施形態に即して説明する。
本発明のゴムシール用表面処理液（以下、単に「表面処理液」または「処理液」とも略称する。）は、
（Ａ）塩素化イソシアヌル酸（以下、「（Ａ）成分」ともいう。）、
（Ｂ）第３級アルコール系溶媒（以下、「（Ｂ）成分」ともいう。）、並びに
（Ｃ）エステル系溶媒および／またはケトン系溶媒（以下、「（Ｃ）成分」ともいう。）
を含むことが、主たる特徴である。
Hereinafter, the present invention will be described with reference to preferred embodiments thereof.
The surface treatment liquid for rubber seal of the present invention (hereinafter simply referred to as “surface treatment liquid” or “treatment liquid”)
(A) Chlorinated isocyanuric acid (hereinafter also referred to as “component (A)”),
(B) Tertiary alcohol solvent (hereinafter also referred to as “component (B)”), and (C) Ester solvent and / or ketone solvent (hereinafter also referred to as “(C) component”).
It is the main feature to contain.
［（Ａ）塩素化イソシアヌル酸］
本発明において、「塩素化イソシアヌル酸」とは、塩素化イソシアヌル酸の塩も含む概念であり、例えば、トリクロロイソシアヌル酸、ジクロロイソシアヌル酸、ジクロロイソシアヌル酸ナトリウム及びその水和物、ジクロロイソシアヌル酸カリウム、ジクロロイソシアヌル酸カルシウム、ジクロロイソシアヌル酸マグネシウム等が挙げられる。なかでも、低摩擦性付与効果の観点からトリクロロイソシアヌル酸が特に好ましい。塩素化イソシアヌル酸は１種または２種以上を使用できる。
[(A) Chlorinated isocyanuric acid]
In the present invention, "chlorinated isocyanuric acid" is a concept that includes salts of chlorinated isocyanuric acid, for example, trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate and hydrates thereof, potassium dichloroisocyanurate, Examples include calcium dichloroisocyanurate and magnesium dichloroisocyanurate. Of these, trichloroisocyanuric acid is particularly preferable from the viewpoint of the effect of imparting low friction. 1 type (s) or 2 or more types can be used for chlorinated isocyanuric acid.
処理液中の塩素化イソシアヌル酸の含有量は、処理液全体当たり１〜１０重量％が好ましく、より好ましくは２〜５重量％である。１０重量％より多いと、ゴムシールの伸張性を低下させる傾向となり、１重量％未満ではゴムシール表面に十分な低摩擦性を付与することが困難な傾向となる。特に、２〜５重量％であれば、伸張性の維持効果（伸張性低下の抑制効果）、低摩擦性の付与効果および防着性の付与効果のバランスのよい処理液となる。 The content of chlorinated isocyanuric acid in the treatment liquid is preferably 1 to 10% by weight, more preferably 2 to 5% by weight, based on the whole treatment liquid. If the amount is more than 10% by weight, the extensibility of the rubber seal tends to be lowered, and if it is less than 1% by weight, it tends to be difficult to impart sufficient low friction to the rubber seal surface. In particular, when the content is 2 to 5% by weight, the treatment liquid has a good balance between the effect of maintaining extensibility (the effect of suppressing the decrease in extensibility), the effect of imparting low friction, and the effect of imparting adhesion.
［（Ｂ）第３級アルコール系溶媒］
第３級アルコール系溶媒は、本発明の処理液を室温処理にて所期の効果が得られる処理液とする観点から、炭素数が５〜１０程度の第３級アルコール系溶媒が好ましく、例えば、ｔｅｒｔ−アミルアルコール、ｔｅｒｔ−ヘプチルアルコール等が挙げられ、好ましくはｔｅｒｔ−アミルアルコールである。第３級アルコール系溶媒は１種または２種以上を使用できる。
[(B) Tertiary alcohol solvent]
The tertiary alcohol-based solvent is preferably a tertiary alcohol-based solvent having about 5 to 10 carbon atoms from the viewpoint that the processing solution of the present invention is a processing solution that can achieve the desired effect at room temperature. Tert-amyl alcohol, tert-heptyl alcohol and the like, preferably tert-amyl alcohol. One or more tertiary alcohol solvents can be used.
［（Ｃ）エステル系溶媒および／またはケトン系溶媒］
エステル系溶媒としては、例えば、酢酸エチル、酢酸ブチル等が挙げられ、好ましくは、酢酸エチルである。また、ケトン系溶媒としては、例えば、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、ジイソブチルケトン（ＤＩＢＫ）、シクロヘキサノン、ジアセトンアルコール（ＤＡＡ）等が挙げられ、好ましくは、アセトン、メチルエチルケトン（ＭＥＫ）である。エステル系溶媒およびケトン系溶媒は、それぞれ、１種または２種以上を使用できる。
[(C) Ester solvent and / or ketone solvent]
Examples of the ester solvent include ethyl acetate and butyl acetate, with ethyl acetate being preferred. Examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone, diacetone alcohol (DAA), and the like. Preferably, acetone, methyl ethyl ketone ( MEK). One type or two or more types of ester solvents and ketone solvents can be used, respectively.
当該（Ｃ）成分の好ましい態様は、エステル系溶媒の単独、或いは、エステル系溶媒とケトン系溶媒の併用である。エステル系溶媒とケトン系溶媒の併用の場合、エステル系溶媒とケトン系溶媒の量比（エステル系溶媒：ケトン系溶媒）は重量比で１：１〜２程度が好ましい。 A preferred embodiment of the component (C) is an ester solvent alone or a combination of an ester solvent and a ketone solvent. When the ester solvent and the ketone solvent are used in combination, the weight ratio of the ester solvent and the ketone solvent (ester solvent: ketone solvent) is preferably about 1: 1 to 2.
（Ｂ）第３級アルコール系溶媒を使用せず、（Ａ）塩素化イソシアヌル酸を（Ｃ）エステル系溶媒および／またはケトン系溶媒に溶解させて得られる処理液の場合、処理液がゴムシールの内部に浸透して、ゴムシールの伸張性が低下してしまう。このため、ゴムシールが引き伸ばされると、表面に亀裂を発生し、シール性能を維持できなくなる。一方、（Ｃ）エステル系溶媒および／またはケトン系溶媒を使用せず、（Ａ）塩素化イソシアヌル酸を（Ｂ）第３級アルコール系溶媒に溶解させて得られる処理液の場合、ゴムシールの伸張性は低下させないものの、十分に高い防着性の付与効果を得ることが困難になる。 In the case of a treatment liquid obtained by dissolving (B) a tertiary alcohol solvent and (A) chlorinated isocyanuric acid in (C) an ester solvent and / or a ketone solvent, the treatment liquid is a rubber seal. It penetrates into the interior and the extensibility of the rubber seal is reduced. For this reason, when the rubber seal is stretched, a crack is generated on the surface, and the sealing performance cannot be maintained. On the other hand, in the case of a treatment solution obtained by dissolving (A) a chlorinated isocyanuric acid in (B) a tertiary alcohol solvent without using (C) an ester solvent and / or a ketone solvent, the rubber seal is extended. However, it is difficult to obtain a sufficiently high adhesion-preventing effect.
本発明の表面処理液において、（Ｂ）第３級アルコール系溶媒と（Ｃ）エステル系溶媒および／またはケトン系溶媒との配合比（（Ｂ）：（Ｃ））は、重量比で５：５〜８：２が好ましく、６：４〜７：３がより好ましい。 In the surface treatment liquid of the present invention, the blending ratio of (B) tertiary alcohol solvent to (C) ester solvent and / or ketone solvent ((B) :( C)) is 5: 5-8: 2 is preferable, and 6: 4-7: 3 is more preferable.
本発明の表面処理液には、本発明の効果を損なわない範囲で、（Ｂ）成分および（Ｃ）成分以外の溶媒をさらに配合してもよい。 You may further mix | blend the solvent other than (B) component and (C) component in the surface treatment liquid of this invention in the range which does not impair the effect of this invention.
本発明はゴムシールの表面を簡易に改質することを目的としており、本発明の処理液は、室温保存において、（Ａ）塩素化イソシアヌル酸が溶解状態にあることが好ましい。処理液中に（Ａ）塩素化イソシアヌル酸の沈殿や析出物がある場合、所期の処理効果が得られ難くなる。 The object of the present invention is to easily modify the surface of the rubber seal, and the treatment liquid of the present invention preferably has (A) chlorinated isocyanuric acid in a dissolved state when stored at room temperature. When (A) chlorinated isocyanuric acid precipitates or deposits are present in the treatment liquid, it is difficult to obtain the desired treatment effect.
ゴムシールの表面に、本発明の処理液を付す（接触させる）方法は特に限定されないが、ゴムシールを処理液中に浸漬する処理、ゴムシールに処理液をスプレー塗布する処理、はけ塗り等が挙げられるが、作業が簡易で、短時間で効果が得られるという観点から、浸漬処理が好ましい。浸漬時間は１〜２０分程度が好ましく、より好ましくは１〜１０分程度である。２０分を超えると、処理液がゴムシール内部に浸透してゴムシールの伸張性を低下させる傾向となる。浸漬後は、水またはアルコール等の有機溶媒に数秒程度浸すことでゴム表面の処理液を洗浄し、その後取り出して室温で自然乾燥させる。 The method for applying (contacting) the treatment liquid of the present invention to the surface of the rubber seal is not particularly limited, and examples include a process of immersing the rubber seal in the treatment liquid, a process of spraying the treatment liquid onto the rubber seal, and brushing. However, the immersion treatment is preferable from the viewpoint that the operation is simple and the effect can be obtained in a short time. The immersion time is preferably about 1 to 20 minutes, more preferably about 1 to 10 minutes. If it exceeds 20 minutes, the treatment liquid tends to penetrate into the rubber seal and reduce the extensibility of the rubber seal. After the immersion, the rubber surface treatment solution is washed by immersing in an organic solvent such as water or alcohol for about several seconds, and then taken out and naturally dried at room temperature.
本発明の表面処理液は、ゴム成分が、天然ゴム、ニトリルゴム（ＮＢＲ）、エチレン−プロピレンゴム、クロロプレンゴム、シリコーンゴム、フッ素ゴム等からなる、種々のゴムシールの表面改質に適用でき、また、処理対象のゴムシールは未加硫ゴムの成形体であっても加硫ゴムの成形体のいずれであってもよい。ゴムシールが、ニトリルゴム（ＮＢＲ）を含むゴムシールの場合、本発明の表面処理液にて表面改質を行うことで、ニトリルゴム（ＮＢＲ）が有する優れた耐油性及び機械的特性を活かしつつ、運動部の摺動性を維持し得る摺動部用シールを実現できる。 The surface treatment liquid of the present invention can be applied to the surface modification of various rubber seals in which the rubber component is composed of natural rubber, nitrile rubber (NBR), ethylene-propylene rubber, chloroprene rubber, silicone rubber, fluororubber, etc. The rubber seal to be treated may be either an unvulcanized rubber molded body or a vulcanized rubber molded body. When the rubber seal is a rubber seal containing nitrile rubber (NBR), by performing surface modification with the surface treatment liquid of the present invention, exercise while utilizing the excellent oil resistance and mechanical properties of nitrile rubber (NBR). A sliding part seal capable of maintaining the sliding property of the part can be realized.
なお、本発明でいう「ゴムシール」とは、ゴムを主成分とするシール（成形体）であり、特に限定はされないが、一般的には、シール（成形体）全体の少なくとも３０重量％以上がゴム成分からなるシールを意味する。 The “rubber seal” as used in the present invention is a seal (molded product) mainly composed of rubber, and is not particularly limited, but generally, at least 30% by weight or more of the entire seal (molded product) is used. It means a seal made of a rubber component.
以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明は以下の実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited at all by the following examples.
実施例１〜４
（処理液の調製）
（Ａ）塩素化イソシアヌル酸としてトリクロロイソシアヌル酸を、（Ｂ）第３級アルコール系溶媒としてｔｅｒｔ−アミルアルコール（以下、「ｔＡＡ」とも略称する）を、（Ｃ）エステル系溶媒および／またはケトン系溶媒として酢酸エチル（以下、「ＥＡ」とも略称する）をそれぞれ使用し、溶媒となるｔＡＡとＥＡの配合比がｔＡＡ：ＥＡ＝８：２、７：３、６：４及び５：５の４通りとなるように、かつその各々に溶解しているトリクロロイソシアヌル酸が２重量％となるように配合した４種類の処理液を、それぞれ均一に溶解するまで混合・撹拌して調整した。
Examples 1-4
(Preparation of treatment solution)
(A) Trichloroisocyanuric acid as chlorinated isocyanuric acid, (B) tert-amyl alcohol (hereinafter also abbreviated as “tAA”) as tertiary alcohol solvent, (C) ester solvent and / or ketone system Ethyl acetate (hereinafter also abbreviated as “EA”) is used as a solvent, and the blending ratio of tAA and EA serving as a solvent is 4 of tAA: EA = 8: 2, 7: 3, 6: 4 and 5: 5. Four kinds of treatment liquids were blended so as to be as they were and mixed so that trichloroisocyanuric acid dissolved in each of them was 2% by weight, and mixed and stirred until they were uniformly dissolved.
（試料）
ゴム成分がＮＢＲからなるシート状に加硫成形した成形体を５０ｍｍ（縦）×２０ｍｍ（横）×２ｍｍ（厚さ）に加工し、作製した。
(sample)
A molded body obtained by vulcanizing and molding the rubber component into a sheet made of NBR was processed to a size of 50 mm (length) × 20 mm (width) × 2 mm (thickness).
（処理方法）
処理液中に上記の試験片を所定時間（１分、５分、１０分）浸漬後、洗浄、乾燥処理して、表面改質を行った。
(Processing method)
The test piece was immersed in the treatment liquid for a predetermined time (1 minute, 5 minutes, 10 minutes), then washed and dried to perform surface modification.
比較例１
溶媒をＥＡのみに変更して処理液を調製した以外は実施例と同様にして表面改質を行った。
Comparative Example 1
Surface modification was performed in the same manner as in Example except that the treatment liquid was prepared by changing the solvent to EA only.
比較例２
溶媒をｔＡＡのみに変更して処理液を調製した以外は実施例と同様にして表面改質を行った。
Comparative Example 2
Surface modification was performed in the same manner as in Example except that the treatment liquid was prepared by changing the solvent to tAA only.
以上、作製した実施例１〜４、比較例１、２のゴム部材（試料）に対して下記の評価試験を実施した。 The following evaluation tests were performed on the rubber members (samples) of Examples 1 to 4 and Comparative Examples 1 and 2 thus manufactured.
［評価試験］
（１）摩擦試験（静摩擦係数及び動摩擦係数の測定）
ＪＩＳ Ｋ７１２５を参考にＨＥＩＤＯＮ社製の表面性測定器を用いた。水平な試験テーブル上で試験片（任意サイズ）にボール圧子（ＳＵＳ３０４）を接点に１００ｇの荷重をかけ、７５ｍｍ／ｍｉｎで試験片を水平に動かした際のボール圧子と試験片間の摩擦係数を測定した。
[Evaluation test]
(1) Friction test (measurement of static friction coefficient and dynamic friction coefficient)
A surface property measuring instrument manufactured by HEIDON was used with reference to JIS K7125. Apply a ball indenter (SUS304) to the test piece (arbitrary size) on the horizontal test table and apply a load of 100 g to the contact point, and the coefficient of friction between the ball indenter and the test piece when the test piece is moved horizontally at 75 mm / min. It was measured.
（２）防着性試験
試験片の処理表面同士を接触させて上から１ｋｇ程度の荷重を５分程度かけ、荷重を取り除いた際に、試験片同士が付着しており、多少の振動を与えたり振ったりしても全く分離しない場合を不可（×）、付着はしているが、軽く振動を与えたり振ったりすれば分離する場合を可（△）、付着していない場合を良好（○）とした。
(2) Anti-adhesion test When the treated surfaces of the test pieces are brought into contact with each other, a load of about 1 kg is applied for about 5 minutes from the top, and when the load is removed, the test pieces adhere to each other and give some vibration. If it does not separate at all even if it shakes or shakes, it is impossible (×), but it adheres, but if it is lightly shaken or shaken, it can be separated (△), and it does not adhere (○ ).
（３）伸張性試験
試験片を１００％〜１５０％程度伸張させ、その表面を目視で観察して亀裂が認められるものを不可（×）、目視では亀裂は全く認められないが、その表面をマイクロスコープ（２００倍）で観察した場合に認められるものを可（△）、２００倍でも亀裂が認められないものを良好（○）とした。
(3) Stretchability test The test piece is stretched by about 100% to 150%, and the surface is visually observed to make cracks impossible (×). What was observed when observed with a microscope (200 times) was acceptable (Δ), and what was not observed even at 200 times was judged good (◯).
下記表１〜６が試験結果である。 The following Tables 1 to 6 are test results.
上記の表１〜６の結果から、本発明の表面処理液であれば、ゴムシールに対して、伸張性を低下させることなく、低摩擦性および防着性を付与できることが分かる。 From the results of Tables 1 to 6 above, it can be seen that the surface treatment liquid of the present invention can impart low friction and adhesion to the rubber seal without reducing extensibility.
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| EP3715406A1 (en) * | 2019-03-29 | 2020-09-30 | Henkel AG & Co. KGaA | Process for modifying the surface polarity of rubber substrates |
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