JP2827402B2 - Surface treatment agent for vulcanized rubber - Google Patents
Surface treatment agent for vulcanized rubberInfo
- Publication number
- JP2827402B2 JP2827402B2 JP2049096A JP4909690A JP2827402B2 JP 2827402 B2 JP2827402 B2 JP 2827402B2 JP 2049096 A JP2049096 A JP 2049096A JP 4909690 A JP4909690 A JP 4909690A JP 2827402 B2 JP2827402 B2 JP 2827402B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- polybutadiene
- weight
- vulcanized rubber
- surface treatment
- 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.)
- Expired - Lifetime
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、加硫ゴム用表面処理剤に関する。更に詳し
くは、ゴム被覆金属製ガスケットのゴム被覆層などに有
効に適用される加硫ゴム用表面処理剤に関する。Description: TECHNICAL FIELD The present invention relates to a surface treatment agent for vulcanized rubber. More specifically, the present invention relates to a surface treatment agent for vulcanized rubber which is effectively applied to a rubber coating layer of a rubber-coated metal gasket.
従来から、ゴム被覆金属製ガスケットの表面には、固
着防止および耐摩耗性向上という目的で、グラファイト
のコーティング膜を形成させることが行われているが、
エンジンガスケットなどの高面圧、高温度使用条件下で
更にエンジンの振動が加わると、ガスケット表面のゴム
被覆層が摩耗し、ガス洩れを発生させることがある。Conventionally, a graphite coating film has been formed on the surface of a rubber-coated metal gasket for the purpose of preventing sticking and improving wear resistance.
When the engine is further vibrated under conditions of high surface pressure and high temperature such as an engine gasket, the rubber coating layer on the surface of the gasket is worn, which may cause gas leakage.
これらの摩耗に関連する原因としては、グラファイト
コーティング膜のグラファイト粒子を固めているバイン
ダー樹脂の強度とグラファイトとの配合比の問題があ
り、一般にはグラファイトの滑り特性を保持するため
に、グラファイトをバインダー樹脂の約２〜４倍量程度
配合する必要があり、そのためにバインダー強度が低下
して、高面圧下では摩耗したり、破壊したりするような
現象がみられる。The causes related to these abrasions include the strength of the binder resin that solidifies the graphite particles of the graphite coating film and the mixing ratio with graphite.In general, to maintain the sliding properties of graphite, graphite is used as a binder. It is necessary to mix the resin in an amount of about 2 to 4 times the amount of the resin, and as a result, a phenomenon that the strength of the binder is reduced and the resin is worn or broken under a high surface pressure is observed.
本発明の目的は、エンジンヘッドガスケットの使用環
境である高面圧、高温度に更に振動が加わるような苛酷
な条件下においても、ガスケット表面のゴム被覆層に摩
耗や破壊を生ずる現象が殆んどみられず、ガスシールに
有効なガスケットなどを形成させ得る加硫ゴム用表面処
理剤を提供することにある。It is an object of the present invention that the rubber coating layer on the gasket surface rarely wears or breaks even under severe conditions where vibration is further applied to the high surface pressure and high temperature, which are the operating environment of the engine head gasket. An object of the present invention is to provide a surface treating agent for vulcanized rubber which can form a gasket or the like effective for gas sealing.
かかる本発明の目的は、液状1,2−ポリブタジエンの
水酸基含有物およびその硬化剤としての1,2−ポリブタ
ジエンイソシアネート化物に、これら両者の合計100重
量部当り固形分として約30〜150重量部のポリオレフィ
ン樹脂の水性分散液を添加した加硫ゴム用表面処理剤に
よって達成される。The object of the present invention is to provide a hydroxyl-containing material of liquid 1,2-polybutadiene and a 1,2-polybutadiene isocyanate as a curing agent thereof in an amount of about 30 to 150 parts by weight as a solid content per 100 parts by weight of both of them. This is achieved by a surface treating agent for vulcanized rubber to which an aqueous dispersion of a polyolefin resin is added.
液状1,2−ポリブタジエンの水酸基含有物は、分子量
約1000程度の液状1,2−ポリブタジエンの両末端に第１
ヒドロキシルグリコールを付加させ、これを更に加熱中
エアーにてボイル変性して、OH価を約100〜120（mgKOH/
g）にしたものであって、本発明にあっては市販品、例
えば日本曹達製品日曹ポリブタGQ1000（45重量％キシレ
ン溶液として市販されている）などをそのまま用いるこ
とができる。The hydroxyl group-containing substance of liquid 1,2-polybutadiene has a first terminal at both ends of liquid 1,2-polybutadiene having a molecular weight of about 1,000.
Hydroxyl glycol was added, and this was further subjected to boil denaturation with air during heating to make the OH value about 100 to 120 (mgKOH /
g), and in the present invention, a commercially available product, for example, Nippon Soda product Nisso Polybuta GQ1000 (commercially available as a 45% by weight xylene solution) can be used as it is.
また、これの硬化剤として用いられる1,2−ポリブタ
ジエンイソシアネート化物は、分子量約1000程度の液状
1,2−ポリブタジエンの両末端にトリメチロールプロパ
ントリイソシアネートなどのポリイソシアネートを付加
させた多官能性のウレタンプレポリマーであって、本発
明にあってはやはり市販品、例えば日本曹達製品日曹ポ
リブタTP1001（50重量％酢酸ブチル溶液として市販され
ている）などをそのまま用いることができる。この1,2
−ポリブタジエンイソシアネート化物は、1,2−ポリブ
タジエン水酸基含有物の水酸基に反応する硬化剤とし
て、一般に等重量で用いられる。In addition, 1,2-polybutadiene isocyanate used as a curing agent is a liquid having a molecular weight of about 1,000.
A polyfunctional urethane prepolymer obtained by adding a polyisocyanate such as trimethylolpropane triisocyanate to both ends of 1,2-polybutadiene, which is also a commercial product in the present invention, for example, Nisso Polybuta product from Nippon Soda TP1001 (commercially available as a 50% by weight butyl acetate solution) or the like can be used as it is. These 1,2
The polybutadiene isocyanate is generally used in an equal weight as a curing agent which reacts with the hydroxyl group of the 1,2-polybutadiene hydroxyl group-containing material.
本発明の表面処理剤においては、ポリオレフィン樹脂
の水性分散液が更に添加されている。このポリオレフィ
ン樹脂の水性分散液は、環球法軟化点が約110〜150℃の
高分子量ポリオレフィン樹脂を粒径約５μ以下、好まし
くは約２〜３μの球状の粒子状態で界面活性剤を用いず
に水性分散液として調製したものであり、例えば三井石
油化学製品ケミパールＷシリーズなどとして市販されて
おり、本発明においてはかかる市販品をそのまま用いる
ことができる。In the surface treatment agent of the present invention, an aqueous dispersion of a polyolefin resin is further added. The aqueous dispersion of the polyolefin resin is obtained by using a high molecular weight polyolefin resin having a ring and ball softening point of about 110 to 150 ° C. in a spherical particle state having a particle diameter of about 5 μm or less, preferably about 2 to 3 μ without using a surfactant. It is prepared as an aqueous dispersion, and is commercially available, for example, as Mitsui Petrochemical's Chemipearl W series. In the present invention, such a commercially available product can be used as it is.
かかる水性分散液は、1,2−ポリブタジエンの水酸基
含有物およびイソシアネート化物の合計量（固形分）10
0重量部当り固形分として約30〜150重量部、好ましくは
約40〜120重量部の割合で用いられる。その添加割合が
これ以下では、本発明の目的とする耐摩耗性の改善効果
がみられず、一方これより多い割合で用いると、バイン
ダーである1,2−ポリブタジエンの結合強度が少しずつ
低下し、摩耗量が増加するようになる。Such an aqueous dispersion has a total amount (solid content) of the hydroxyl group-containing material and isocyanate of 1,2-polybutadiene of 10%.
It is used in a proportion of about 30 to 150 parts by weight, preferably about 40 to 120 parts by weight as a solid content per 0 parts by weight. If the addition ratio is less than this, the effect of improving the wear resistance aimed at by the present invention is not seen, while if used at a higher ratio, the bonding strength of 1,2-polybutadiene as the binder decreases gradually. , The amount of wear increases.
表面処理剤の調製は、1,2−ポリブタジエンの水酸基
含有物およびイソシアネート化物にポリオレフィン樹脂
の水性分散液を混合し、ボールミル、スパーミルなどで
ミクロ分散させることによって行われる。そして、必要
に応じてトルエンなどで希釈し、希釈液を用いることに
より、所定の膜厚になるように調整する。その際、水性
分散液は、イソシアネート基の硬化触媒となる。The preparation of the surface treatment agent is carried out by mixing an aqueous dispersion of a polyolefin resin with a hydroxyl group-containing substance and an isocyanate of 1,2-polybutadiene, and microdispersing the mixture with a ball mill, a spar mill or the like. Then, if necessary, the mixture is diluted with toluene or the like, and adjusted to a predetermined film thickness by using a diluent. At that time, the aqueous dispersion becomes a curing catalyst for the isocyanate group.
かかる表面処理剤を用いての表面処理は、加硫ゴム、
例えばそれが金属製ガスケットのゴム被覆層である場合
には、フッ素ゴム、NBR、水添NBR、アクリルゴム、ブチ
ルゴム、エチレン−プロピレン系共重合ゴムなどの加硫
ゴム被覆層上にそれをロールコータなどを用いて塗布
し、約150〜200℃で約２〜30分間程度加熱加硫すること
により行われる。Surface treatment using such a surface treatment agent, vulcanized rubber,
For example, when it is a rubber coating layer of a metal gasket, it is roll-coated on a vulcanized rubber coating layer of fluoro rubber, NBR, hydrogenated NBR, acrylic rubber, butyl rubber, ethylene-propylene copolymer rubber or the like. It is carried out by applying using a method such as the above, and heating and vulcanizing at about 150 to 200 ° C. for about 2 to 30 minutes.
本発明に係る加硫ゴム用表面処理剤は、それを例えば
エンジンヘッドガスケットなど高面圧、高温度に更に振
動が加わるような苛酷な条件下において使用されるゴム
被覆金属製ガスケットのゴム被覆層などに適用した場合
でも、ゴム被覆層に摩耗やゴム破壊が殆んどみられない
というすぐれた効果を奏する。The surface treating agent for vulcanized rubber according to the present invention is a rubber coating layer of a rubber-coated metal gasket which is used under severe conditions such as high pressure and high temperature such as an engine head gasket. Even when applied to a rubber coating layer, the rubber coating layer has an excellent effect that hardly any wear or rubber breakage is observed.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１〜４ 1,2−ポリブタジエン水酸基含有物（日曹ポリブタGQ1
000、50重量％トルエン溶液）100重量部、1,2−ポリブ
タジエンイソシアネート化物（日曹ポリブタTP1001、50
重量％トルエン溶液）100重量部および所定量のポリオ
レフィン樹脂の水性分散液（ケミパールＷ−300;固形分
濃度40重量％、粒径３μ、固形分環球法軟化点132℃、p
H9）の混合物よりなる表面処理剤を、フッ素ゴム加硫成
形品の表面にコーティングし、200℃、９分間の加熱加
硫を行い、膜厚約４〜５μのコーティング膜を形成させ
た。Examples 1 to 4 1,2-polybutadiene hydroxyl-containing material (Nisso Polybutadiene GQ1
000, 50% by weight toluene solution) 100 parts by weight, 1,2-polybutadiene isocyanate (Nisso Polybuta TP1001, 50
Aqueous dispersion of 100 parts by weight of a polyolefin resin and a predetermined amount of a polyolefin resin (Chemipearl W-300; solids concentration 40% by weight, particle size 3 μm, solidification ring-ball method softening point 132 ° C, p
A surface treating agent comprising the mixture of H9) was coated on the surface of the vulcanized molded article of fluororubber, and then heated and vulcanized at 200 ° C. for 9 minutes to form a coating film having a thickness of about 4 to 5 μm.
この表面処理フッ素ゴム加硫成形品について、次の条
件下で鈴木式摩耗試験を行い、その摩耗量を測定した。This surface-treated fluoro rubber vulcanized molded article was subjected to a Suzuki abrasion test under the following conditions, and the amount of abrasion was measured.
温 度：室温 面 圧:3kgf/cm2 回転数 :204rpm 周 速:0.5m/秒 摩耗時間:300秒 得られた結果は、ポリオレフィン樹脂の水性分散液の
使用量と共に、次の表に示される。なお、比較例は、フ
ッ素ゴム加硫成形品表面に膜厚約３〜５μのグラファイ
トコーティング膜を形成させたものについての測定値で
ある。Temperature: room temperature Surface pressure: 3 kgf / cm 2 Number of revolutions: 204 rpm Peripheral speed: 0.5 m / s Wear time: 300 seconds The results obtained are shown in the following table together with the amount of aqueous dispersion of polyolefin resin used. . In addition, the comparative example is a measured value obtained by forming a graphite coating film having a film thickness of about 3 to 5 μm on the surface of a vulcanized molded article of fluororubber.
表 実施例 水性分散液（重量部） 摩耗量（mg） １ 50 28.9
２ 100 0.3
３ 200 2.6
４ 300 5.0
（比較例） 25.0 実施例５ 長方形ガスケットの中心部に孔部を設け、その孔部の
周辺を一定の幅で一定の深さに陥没させたフッ素ゴム被
覆FKM材製ガスケットについて、高面圧下での10万回強
制変位による強制変位試験（変位量0.5mm、1Hz、120
℃）を行い、フッ素ゴム被覆層の状態を目視で観察し
た。Table Example Aqueous dispersion (parts by weight) Abrasion amount (mg) 1 50 28.9
2 100 0.3
3 200 2.6
4 300 5.0
(Comparative Example) 25.0 Example 5 A gasket made of a fluoro rubber-coated FKM material in which a hole was provided at the center of a rectangular gasket and the periphery of the hole was depressed to a certain width and a certain depth under a high surface pressure Displacement test with 100,000 times of forced displacement (displacement 0.5mm, 1Hz, 120
° C), and the state of the fluororubber coating layer was visually observed.
上記実施例２の表面処理剤で表面処理されたフッ素ゴ
ム被覆層は、面圧1000kg/cm2または2000kg/cm2でも摩耗
がみられなかったが、上記比較例のグラファイト表面処
理されたフッ素ゴム被覆層は、面圧1000kg/cm2で摩耗を
発生させ、2000kg/cm2ではゴム破壊を生じた。The fluororubber coating layer surface-treated with the surface treating agent of Example 2 did not show any abrasion even at a surface pressure of 1000 kg / cm 2 or 2000 kg / cm 2 , but the graphite surface-treated fluororubber of the comparative example described above. coating layer may generate wear at a surface pressure of 1000 kg / cm 2, resulting in a rubber destruction in 2000 kg / cm 2.
Claims (2)
およびその硬化剤としての1,2−ポリブタジエンイソシ
アネート化物に、これら両者の合計100重量部当り固形
分として約30〜150重量部のポリオレフィン樹脂の水性
分散液を添加してなる加硫ゴム用表面処理剤。1. A polyolefin resin having a solid content of about 30 to 150 parts by weight per 100 parts by weight of a total of a liquid 1,2-polybutadiene hydroxyl-containing substance and a 1,2-polybutadiene isocyanate as a curing agent thereof. A surface treating agent for vulcanized rubber obtained by adding an aqueous dispersion of
適用される請求項１記載の加硫ゴム用表面処理剤。2. The surface treating agent for vulcanized rubber according to claim 1, which is applied to a rubber coating layer of a rubber-coated metal gasket.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049096A JP2827402B2 (en) | 1990-02-28 | 1990-02-28 | Surface treatment agent for vulcanized rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049096A JP2827402B2 (en) | 1990-02-28 | 1990-02-28 | Surface treatment agent for vulcanized rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03252442A JPH03252442A (en) | 1991-11-11 |
| JP2827402B2 true JP2827402B2 (en) | 1998-11-25 |
Family
ID=12821566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2049096A Expired - Lifetime JP2827402B2 (en) | 1990-02-28 | 1990-02-28 | Surface treatment agent for vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2827402B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008126741A1 (en) | 2007-04-10 | 2008-10-23 | Nok Corporation | Coating agent |
| KR101823545B1 (en) | 2014-09-22 | 2018-01-30 | 에누오케 가부시키가이샤 | Surface treatment agent for vulcanized rubber |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9732259B2 (en) | 2013-01-08 | 2017-08-15 | Bridgestone Corporation | Laminate and method for producing same |
| JP6302367B2 (en) | 2014-06-24 | 2018-03-28 | ニチアス株式会社 | Coating agent |
| KR101823573B1 (en) | 2014-09-22 | 2018-01-30 | 에누오케 가부시키가이샤 | Surface treatment agent for vulcanized rubber |
| JP6666155B2 (en) | 2016-01-15 | 2020-03-13 | ニチアス株式会社 | Coating agent, surface-coated elastic body and surface-coated rubber metal laminate |
| JP2018091261A (en) | 2016-12-06 | 2018-06-14 | ニチアス株式会社 | Coating agent for rubber-coated cylinder head gasket, and cylinder head gasket |
-
1990
- 1990-02-28 JP JP2049096A patent/JP2827402B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008126741A1 (en) | 2007-04-10 | 2008-10-23 | Nok Corporation | Coating agent |
| KR101823545B1 (en) | 2014-09-22 | 2018-01-30 | 에누오케 가부시키가이샤 | Surface treatment agent for vulcanized rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03252442A (en) | 1991-11-11 |
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