JPH086076B2 - Rubber adhesive composition - Google Patents
Rubber adhesive compositionInfo
- Publication number
- JPH086076B2 JPH086076B2 JP28633887A JP28633887A JPH086076B2 JP H086076 B2 JPH086076 B2 JP H086076B2 JP 28633887 A JP28633887 A JP 28633887A JP 28633887 A JP28633887 A JP 28633887A JP H086076 B2 JPH086076 B2 JP H086076B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- adhesive composition
- based adhesive
- adherend
- compound
- 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 - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 76
- 239000005060 rubber Substances 0.000 title claims description 76
- 230000001070 adhesive effect Effects 0.000 title claims description 68
- 239000000853 adhesive Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 60
- -1 organic polysulfide compound Chemical class 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 8
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical group CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004636 vulcanized rubber Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- 150000008117 polysulfides Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】 Ｉ 技術分野 本発明はゴム系の被接着体を相互に接着するゴム系接
着剤組成物に関し、より詳しくは、加硫ゴムの被接着体
と未加硫ゴムの被接着体とを耐熱性良好に強力に接着す
るゴム系接着剤組成物に関する。Description: TECHNICAL FIELD The present invention relates to a rubber-based adhesive composition for adhering rubber-based adherends to each other, and more specifically, to a vulcanized rubber-adhered body and an unvulcanized rubber-covered body. The present invention relates to a rubber-based adhesive composition that strongly adheres to an adhesive with good heat resistance.
II 従来技術 ゴム製ベルトの両端を相互に接着してエンドレスベル
トとする場合のように、ゴム系の被接着体を相互に接着
する場合、一般に第１図に示すように被接着体である加
硫ゴム１相互の間に接着剤組成物２を介して被接着体の
未加硫ゴム３を配し、それらを加熱圧着する。そして、
この接着剤組成物２としては、通常、共セメントと称さ
れる被接着体ゴムの未加硫ゴムを溶剤で溶かしたものが
使用されている。II Prior Art When a rubber-based adherend is adhered to each other, as in the case where both ends of a rubber belt are adhered to each other to form an endless belt, generally, as shown in FIG. The unvulcanized rubber 3 to be adhered is placed between the vulcanized rubbers 1 with the adhesive composition 2 interposed therebetween, and they are heat-pressed. And
As the adhesive composition 2, a material obtained by dissolving an unvulcanized rubber of an adherend rubber called co-cement with a solvent is usually used.
しかしながら、共セメントを使用すると接着面の耐熱
性を被接着体本体と同程度以上にすることができないと
いうこと等の問題点がある。However, when co-cement is used, there is a problem in that the heat resistance of the adhesive surface cannot be made equal to or higher than that of the adherend body.
例えば、被接着体がジエン系主体のゴムである場合に
は、一般にその耐熱性を向上させるため、被接着体ゴム
の加硫としては低硫黄含量の加硫がなされる。そしてこ
の場合、低硫黄量の加硫剤としてはチウラム系加硫促進
剤等の低硫黄−高加硫促進剤が添加される（所謂EV加
硫）。しかし、被接着体がこのようなEV加硫系である場
合には、硫黄含量が低いため通常の共セメントを接着剤
組成物としても接着することはできない。For example, when the adherend is a rubber mainly composed of a diene, the rubber to be adhered is generally vulcanized with a low sulfur content in order to improve its heat resistance. In this case, a low sulfur-high vulcanization accelerator such as a thiuram vulcanization accelerator is added as a vulcanization agent having a low sulfur content (so-called EV vulcanization). However, when the adherend is such an EV vulcanization system, since the sulfur content is low, ordinary co-cement cannot be adhered even as an adhesive composition.
そこで、EV加硫系ゴムの接着には、接着剤組成物とし
て通常の共セメントではなく、共セメントにイオウまた
は種々のイオウ供与体を添加したものか、あるいは被接
着体のポリマーと異種のポリマーであるが被接着体ゴム
との組合せにより高接着性を発揮するポリマー（例え
ば、被接着体がSBRである場合のセメントとしてのNR）
から調整される接着性組成物が使用されている。Therefore, for the adhesion of EV vulcanized rubber, not the usual co-cement as an adhesive composition, but one obtained by adding sulfur or various sulfur donors to the co-cement, or a polymer different from the polymer of the adherend However, a polymer that exhibits high adhesiveness when combined with rubber to be adhered (for example, NR as cement when the adherend is SBR)
An adhesive composition prepared from
しかしながら、これらの接着剤組成物を使用すると接
着物の耐熱性が低くなり、また接着界面の接着力の寿命
が短くなるという問題点がある。さらに、これらの接着
剤組成物は通常の共セメントに比べて高硫黄含有組成物
となっているのでゲル化しやすく、接着剤組成物自体の
寿命が短いという問題点もある。However, when these adhesive compositions are used, there are problems that the heat resistance of the adhesive becomes low and the life of the adhesive force at the adhesive interface becomes short. Furthermore, since these adhesive compositions are high-sulfur content compositions as compared with ordinary co-cement, they tend to gel and the adhesive composition itself has a short life.
そこで、被接着体がEV加硫系ゴムであっても高耐熱性
に接着することができ、しかも接着剤組成物自体の寿命
も長い接着剤組成物の開発が望まれていた。Therefore, it has been desired to develop an adhesive composition that can be adhered with high heat resistance even when the adherend is an EV vulcanized rubber and that the adhesive composition itself has a long life.
III 発明の目的 本発明は前記従来技術に伴う問題点を解決しようとす
るものであって、本発明の目的は、ゴム系の被接着体を
相互に接着させるに際し、加硫ゴム被接着本体と未加硫
ゴムとの接着面に加硫ゴム被接着体本体と同程度以上の
耐熱性を付与することができるゴム系接着剤組成物、特
に、被接着体がEV加硫系ゴムであっても高耐熱性に接着
することができるゴム系接着剤組成物を提供すること、
さらに、その組成物自体の寿命が長いゴム系接着剤組成
物を提供することにある。III Object of the Invention The present invention is intended to solve the problems associated with the above-mentioned prior art, and an object of the present invention is to bond a vulcanized rubber adhered body with a rubber-based adherend to each other. A rubber-based adhesive composition capable of imparting heat resistance equal to or higher than that of the main body of the vulcanized rubber to be adhered to the surface to be adhered to the unvulcanized rubber, in particular, the adherend is an EV vulcanized rubber. Also to provide a rubber-based adhesive composition capable of bonding with high heat resistance,
Another object of the present invention is to provide a rubber-based adhesive composition having a long service life.
IV 発明の構成 本発明者は上記目的を達成すべく鋭意努力した結果、
共セメント等の如く未加硫ゴムを溶剤で溶かしたもの
に、さらに特定の有機ポリサルファイド化合物を含有さ
せると接着力及び接着面の耐熱性が飛躍的に向上するこ
とを見い出し本発明を完成させるに至った。IV Structure of the Invention As a result of the earnest efforts of the inventor to achieve the above object,
In order to complete the present invention, it was found that when unvulcanized rubber is dissolved in a solvent such as co-cement etc., and further containing a specific organic polysulfide compound, the adhesive strength and the heat resistance of the adhesive surface are dramatically improved. I arrived.
即ち、本発明のゴム、分子の少なくとも一つの末端が
アルコキシシラン基である有機ポリサルフアイド化合
物、及び溶剤を含有してなるゴム系接着剤組成物を提供
する。That is, there is provided a rubber-based adhesive composition containing the rubber of the present invention, an organic polysulfide compound having at least one terminal of its molecule an alkoxysilane group, and a solvent.
上記発明においては前記ゴムが被接着体ゴムと同質の
ゴムであるのが好ましい。In the above invention, it is preferable that the rubber is of the same quality as the adherend rubber.
また、前記有機ポリサルファイド化合物の少なくとも
一つの末端のアルコキシシラン基がトリメトキシシラン
基またはトリエトキシシラン基であるのが好ましい。Moreover, it is preferable that at least one terminal alkoxysilane group of the organic polysulfide compound is a trimethoxysilane group or a triethoxysilane group.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のゴム系接着剤組成物に含有されるゴムとして
は、特に制限的でなく、被接着体を構成するゴムの未加
硫のものの他、一般にゴム系接着剤に使用されるものが
使用できる。The rubber contained in the rubber-based adhesive composition of the present invention is not particularly limited, and unvulcanized rubber constituting the adherend, as well as those generally used in rubber-based adhesives are used. it can.
具体的にはNR、SBR、BR、NBR、CR、IP、EPDM、再生ゴ
ム等をあげることができ、さらにこれらを変性したもの
も含まれる。また、これらのゴム中にはケトン樹脂、ク
マロンインデン樹脂、石油樹脂等の変性用樹脂、炭酸カ
ルシウム、カーボンブラック、ホワイトカーボン、クレ
ー等の補強充填剤、その他のステアリン酸、老化防止
剤、加硫促進剤、硬化剤等が含有されていても良い。な
お、被接着体のゴムを使用すると、被接着体の製造工程
を利用してゴム系接着剤組成物が簡単に調製できるので
好ましい。Specific examples thereof include NR, SBR, BR, NBR, CR, IP, EPDM, recycled rubber, and the like, and those obtained by modifying these are also included. Further, in these rubbers, a modifying resin such as a ketone resin, a coumarone indene resin or a petroleum resin, a reinforcing filler such as calcium carbonate, carbon black, white carbon or clay, other stearic acid, an anti-aging agent, or an additive. A vulcanization accelerator, a curing agent, etc. may be contained. In addition, it is preferable to use the rubber of the adherend because the rubber-based adhesive composition can be easily prepared by utilizing the manufacturing process of the adherend.
本発明に含有される有機ポリサルファイド化合物は、
分子内にポリサルファイド基を有し、かつ分子の少なく
とも一つの末端にアルコキシシラン基を有するものであ
る。ポリサルファイド基あるいはアルコキシシラン基の
いずれか一方だけを有する化合物では本発明の効果を達
成することはできない。The organic polysulfide compound contained in the present invention is
It has a polysulfide group in the molecule and has an alkoxysilane group at at least one end of the molecule. The effect of the present invention cannot be achieved with a compound having only one of a polysulfide group or an alkoxysilane group.
本発明に含有される有機ポリサルファイド化合物とし
ては、具体的には ビス（３−トリエトキシシリルプロピル）−テトラサル
ファイド：（C2H5O）３−Si−（CH2）３−S4−（CH2）
３−Si−（OC2H5）３ トリメトキシシリルプロピル−ベンゾチアジル−テトラ
サルファイド： 等をあげることができる。これらの有機ポリサルファイ
ド化合物のゴム系接着剤組成物における反応理論は詳細
には解明されていないが、100℃以下程度ではイオウを
供与せず、130℃以上程度で良好なイオウ供与体となる
ものである。そして、分子の少なくとも一方の末端にあ
るアルコキシシラン基が遊離イオウの発生を抑制し、そ
れにより、接着面が高硫黄含量で加硫されて低耐熱性に
なることを防止しているものと思われる。The organic polysulfide compound contained in the present invention, specifically, bis (3-triethoxysilylpropyl) - tetrasulfide: (C 2 H 5 O) 3 -Si- (CH 2) 3 -S 4 - ( CH 2 )
3 -Si- (OC 2 H 5) 3 -trimethoxysilylpropyl - benzothiazyl - tetrasulfide: Etc. can be given. The reaction theory of these organic polysulfide compounds in a rubber-based adhesive composition has not been clarified in detail, but it does not donate sulfur at temperatures of 100 ° C or lower, and becomes a good sulfur donor at temperatures of 130 ° C or higher. is there. And it seems that the alkoxysilane group at at least one end of the molecule suppresses the generation of free sulfur, thereby preventing the adhesive surface from being vulcanized with a high sulfur content and becoming low in heat resistance. Be done.
本発明に含有される溶剤としては、トルエン、ｎ−ヘ
キサン、ゴム揮発油、酢酸エチル、メチルエチルケトン
等の各種溶剤が前記ゴムの種類に応じて適宜選択され
る。As the solvent contained in the present invention, various solvents such as toluene, n-hexane, rubber volatile oil, ethyl acetate, and methyl ethyl ketone are appropriately selected according to the kind of the rubber.
次に、上記のようなゴム、有機ポリサルファイド化合
物及び溶剤の配合割合について説明する。Next, the compounding ratio of the rubber, the organic polysulfide compound and the solvent as described above will be described.
ゴムの溶剤溶解物に有機ポリサルファイド化合物が添
加されている本発明のゴム系接着剤組成物は、その有機
ポリサルファイド化合物の配合割合を問わず、有機ポリ
サルファイド化合物が添加されていない接着剤組成物に
比べて優れた接着力と耐熱性を発揮するが、それらの配
合割合はより高い接着力と耐熱性が発揮されるように制
御されるのが好ましい。The rubber-based adhesive composition of the present invention in which the organic polysulfide compound is added to the solvent solution of rubber, regardless of the blending ratio of the organic polysulfide compound, is compared with the adhesive composition in which the organic polysulfide compound is not added. And excellent adhesive strength and heat resistance are exhibited, but it is preferable that the compounding ratio thereof is controlled so that higher adhesive strength and heat resistance are exhibited.
即ち、特に高い接着力が必要とされる場合には、有機
ポリサルファイド化合物として例えばビス（３−トリエ
トキシシリル）テトラサルファイドを使用した場合に
は、その配合割合は、ゴム系接着剤組成物に対して0.5
〜10重量％、より好ましくは２〜８重量％とするのが良
い。この範囲で高い接着力が安定的に得られるからであ
る。一方、10重量％を超えるとゴム系接着剤組成物自体
がゲル化しやすくなるので好ましくなく、また有機ポリ
サルファイド化合物は比較的高価な化合物なので経済的
にも好ましくない。That is, when particularly high adhesive strength is required, for example, when bis (3-triethoxysilyl) tetrasulfide is used as the organic polysulfide compound, the compounding ratio thereof is relative to that of the rubber-based adhesive composition. 0.5
It is good to set it to -10% by weight, more preferably 2-8% by weight. This is because a high adhesive strength can be stably obtained in this range. On the other hand, if it exceeds 10% by weight, the rubber-based adhesive composition itself tends to gel, which is not preferable, and the organic polysulfide compound is also a relatively expensive compound, which is economically undesirable.
本発明のゴム系接着剤組成物は従来の共セメントと同
様に使用される。即ち、第１図に示したように加硫され
ている被接着物ゴム（加硫ゴム１）と未加硫の被接着物
ゴム（未加硫ゴム３）の間に本発明のゴム系接着剤組成
物２を施し、130〜170℃、15〜70分間、面圧8kgf/cm2〜
25kgf/cm2程度で加熱圧着すればよい。The rubber-based adhesive composition of the present invention is used similarly to the conventional co-cement. That is, as shown in FIG. 1, the rubber-based adhesive of the present invention is provided between the vulcanized rubber to be adhered (vulcanized rubber 1) and the unvulcanized rubber to be adhered (unvulcanized rubber 3). Agent composition 2 is applied, 130-170 ° C, 15-70 minutes, surface pressure 8 kgf / cm 2 ~
It may be heated and pressure-bonded at about 25 kgf / cm 2 .
Ｖ 実施例 以下、本発明を実施例により具体的に説明する。V Example Hereinafter, the present invention will be specifically described with reference to Examples.
（実施例１、比較例１〜４） 種々の有機含硫黄化合物の共セメントへの添加テスト （ｉ）ゴム系接着剤組成物の製造 被接着体ゴムとして、以下に示す組成のゴムを150℃
で20分間加硫したものを用意した。(Example 1, Comparative Examples 1 to 4) Addition Test of Various Organic Sulfur-Containing Compounds to Co-Cement (i) Production of Rubber-Based Adhesive Composition As a rubber to be adhered, a rubber having the composition shown below is 150 ° C.
It was prepared by vulcanizing for 20 minutes.
被接着体ゴム組成（重量部） SBR（Nipol1502、日本ゼオン（株）製） 100.0 亜鉛華（正同化学製） 5.0 ステアリン酸（日本油脂製） 1.0 SRFブラック（中部カーボン＃Ｓ） 65.0 芳香族プロセス油（ダイアナプロセスオイル製） 3.0 老防6C（サントフレクス13、モンサント製） 2.0 硫黄 0.3 促進剤（テトラメチル・チウラムダイサルファイド）2.
0促進剤（ジベンゾチアジルダイサルファイド） 1.0 合計 179.3 一方、ゴム系接着剤組成物として上記組成のゴム18重
量％、有機含硫黄化合物として末端にアルコキシシラン
基を有する有機ポリサルファイド化合物であるビス（３
−トリエトキシ シリルプロピル）テトラサルファイド
２重量％、ゴム揮発油80重量％からなる組成物を製造し
た（実施例１）。また有機含硫黄化合物を含有させない
か、あるいはその有機含硫黄化合物として表１表に示す
３種の有機含硫黄化合物を使用した以外は実施例１と同
様にしてゴム系接着剤組成物を製造した（比較例１〜
４）。Rubber composition of adherend (parts by weight) SBR (Nipol1502, manufactured by Nippon Zeon Co., Ltd.) 100.0 Zinc flower (manufactured by Shodo Kagaku) 5.0 Stearic acid (manufactured by NOF Corporation) 1.0 SRF black (Chubu Carbon #S) 65.0 Aromatic Process Oil (manufactured by Diana Process Oil) 3.0 Old 6C (Santoflex 13, manufactured by Monsanto) 2.0 Sulfur 0.3 Accelerator (tetramethyl thiuram disulphide) 2.
0 Accelerator (dibenzothiazyl disulfide ) 1.0 Total 179.3 On the other hand, 18% by weight of the rubber having the above composition as a rubber-based adhesive composition and bis (3) which is an organic polysulfide compound having an alkoxysilane group at the end as an organic sulfur-containing compound.
A composition consisting of 2% by weight of triethoxysilylpropyl) tetrasulfide and 80% by weight of rubber volatile oil was prepared (Example 1). Further, a rubber-based adhesive composition was produced in the same manner as in Example 1 except that the organic sulfur-containing compound was not contained or three kinds of organic sulfur-containing compounds shown in Table 1 were used as the organic sulfur-containing compound. (Comparative Examples 1 to
4).
（ii）接着 上記ゴム系接着剤組成物を、それぞれ加硫した被接着
体ゴムと未加硫の被接着ゴムの間に施し（ゴム厚さ3m
m、接着剤２回ハケ塗り）、150℃、20分、圧力15kgf/cm
2の条件で加硫接合した。(Ii) Adhesion The above rubber-based adhesive composition was applied between the vulcanized rubber to be adhered and the unvulcanized rubber to be adhered (rubber thickness 3 m
m, adhesive applied twice), 150 ℃, 20 minutes, pressure 15kgf / cm
Vulcanization joining was performed under the conditions of 2 .
（iii）剥離試験 上記加硫接合したものを（ａ）常温時、（ｂ）100℃
時、（ｃ）120℃で72時間おくことにより老化させた後
の常温時、（ｅ）120℃で72時間おくことにより老化さ
せた後の100℃時、のそれぞれについてJIS−Ｋ、6854に
準拠してＴ型剥離試験を行った。(Iii) Peeling test The above vulcanized and bonded product (a) at room temperature, (b) 100 ° C
According to JIS-K, 6854, for each time, (c) at room temperature after aging by leaving at 120 ° C for 72 hours, and (e) at 100 ° C after aging at 120 ° C for 72 hours. A T-type peel test was conducted in conformity with the above.
剥離時の剥離力（kgf/2.5cm）および剥離面中の材料
破壊部分占有率（％）を表１にあわせて示す。Table 1 also shows the peeling force (kgf / 2.5cm) at the time of peeling and the material destruction portion occupation ratio (%) in the peeled surface.
（iv）ゴム系接着剤組成物の安定性試験 ゴム系接着剤組成物の安定性を評価するため、40℃で
14日間おいた後のゲルの発生の有無を観察した。(Iv) Stability test of rubber adhesive composition To evaluate the stability of the rubber adhesive composition, at 40 ° C
The presence or absence of gel generation after 14 days was observed.
結果を表１にあわせて示す。 The results are also shown in Table 1.
表１に示した結果より、有機含硫黄化合物が添加され
ている比較例２〜４の組成物は添加されていない比較例
１の組成物よりも常温時には良好な接着性を示すが、加
熱時および老化後の接着性は十分でないこと、および末
端にアルコキシシラン基を有する有機ポリサルファイド
化合物が添加されている本発明の実施例１の組成物は加
熱時および老化後にも良好な接着性を示すことがわか
る。 From the results shown in Table 1, the compositions of Comparative Examples 2 to 4 to which the organic sulfur-containing compound was added exhibited better adhesiveness at room temperature than the composition of Comparative Example 1 to which no organic sulfur-containing compound was added, but when heated. And that the adhesiveness after aging is not sufficient, and that the composition of Example 1 of the present invention in which an organic polysulfide compound having an alkoxysilane group at the end is added exhibits good adhesiveness even after heating and after aging. I understand.
（実施例２および３、比較例５〜７）種々の有機シラン
化合物の共セメントへの添加テスト （ｉ）ゴム系接着剤組成物の製造 実施例１において添加した末端にアルコキシシラン基
を有する有機ポリサルファイド化合物のかわりに表２に
示すポリサルファイド基を有する有機シラン化合物（C.
D）とポリサルファイド基を有さない有機シラン化合物
（A.B）をそれぞれ使用した以外は実施例１と同様にし
てゴム系接着剤組成物を製造した（実施例２、３および
比較例５〜７）。(Examples 2 and 3, Comparative Examples 5 to 7) Addition test of various organic silane compounds to co-cement (i) Production of rubber-based adhesive composition Organic compound having alkoxysilane group at the end added in Example 1 Instead of the polysulfide compound, an organosilane compound having a polysulfide group shown in Table 2 (C.
A rubber-based adhesive composition was produced in the same manner as in Example 1 except that D) and the organosilane compound (AB) having no polysulfide group were used (Examples 2 and 3 and Comparative Examples 5 to 7). .
（ii）接着および剥離試験 上記ゴム系接着剤組成物を使用して実施例１と同様に
接着および剥離試験を行った。(Ii) Adhesion and Peeling Test An adhesion and peeling test was conducted in the same manner as in Example 1 using the above rubber-based adhesive composition.
結果を表２にあわせて示す。 The results are also shown in Table 2.
（iii）ゴム系接着剤組成物の安定性試験 実施例１と同様にしてゲルの発生の有無を観察した。(Iii) Stability test of rubber-based adhesive composition In the same manner as in Example 1, the presence or absence of gel generation was observed.
結果を表２にあわせて示す。 The results are also shown in Table 2.
表２に示した結果より、有機シラン化合物が添加され
ている比較例６、７の組成物は添加されていない比較例
５の組成物よりも老化前は良好な接着性を示すが、老化
後の接着性は常温時、加熱時ともに十分でないこと、お
よびポリサルファイド基を有するシラン化合物が添加さ
れている本発明の実施例２、３の組成物は老化前および
老化後の双方において常温時および加熱時に良好な接着
性を示すことがわかる。 From the results shown in Table 2, the compositions of Comparative Examples 6 and 7 to which the organosilane compound was added exhibited better adhesiveness before aging than the compositions of Comparative Example 5 to which no organosilane compound was added, but after aging The adhesive properties of Nos. 2 and 3 are not sufficient both at room temperature and at the time of heating, and the compositions of Examples 2 and 3 of the present invention to which the silane compound having a polysulfide group is added are heated at room temperature and heated before and after aging. It can be seen that sometimes good adhesion is exhibited.
（実施例４〜10、比較例８）末端にアルコキシシラン基
を有する有機ポリサルファイド化合物の添加量の評価
ゴム系接着剤組成物中の末端にアルコキシシラン基を有
する有機ポリサルファイド化合物の含有量を変化させた
以外は実施例１と同様にして表３に示す８種のゴム系接
着剤組成物を製造した。(Examples 4 to 10, Comparative Example 8) Evaluation of Addition Amount of Organic Polysulfide Compound Having Alkoxysilane Group at Terminal
Eight types of rubber-based adhesive compositions shown in Table 3 were produced in the same manner as in Example 1 except that the content of the organic polysulfide compound having an alkoxysilane group at the terminal in the rubber-based adhesive composition was changed. .
次に、それらのゴム系接着剤組成物を使用して被接着
体の加硫ゴムと未加硫ゴムを実施例１と同様に接着し、
その接着物を120℃で72時間おいて老化させ、その後実
施例１と同様に剥離試験を行った。 Next, using these rubber-based adhesive compositions, the vulcanized rubber and the unvulcanized rubber of the adherend were adhered in the same manner as in Example 1,
The adhesive was aged at 120 ° C. for 72 hours, and then a peel test was conducted in the same manner as in Example 1.
結果を第２図に示す。 Results are shown in FIG.
第２図より、有機ポリサルファイド化合物がビス（３
−トリエトキシ シリルプロピル）テトラサルファイド
である場合、その含有率が２〜８重量％であるとき安定
した高い接着力が得られることがわかる。From FIG. 2, it can be seen that the organic polysulfide compound is bis (3
In the case of -triethoxysilylpropyl) tetrasulfide, it can be seen that stable high adhesive strength can be obtained when the content thereof is 2 to 8% by weight.
VI 発明の効果 本発明のゴム系接着剤組成物を使用して加硫ゴム被接
着体と未加硫ゴムとを加硫接合すれば、常温のみならず
加熱時においても、また老化後においても、強い接着力
を示す耐熱性の接着面を得ることができる。特に、被接
着体がEV加硫系ゴムであるとき、これらの効果は顕著に
発揮される。VI Effect of the Invention By vulcanizing and bonding a vulcanized rubber adherend and an unvulcanized rubber using the rubber-based adhesive composition of the present invention, not only at room temperature but also at the time of heating and also after aging. It is possible to obtain a heat-resistant adhesive surface showing a strong adhesive force. In particular, when the adherend is an EV vulcanized rubber, these effects are remarkably exhibited.
また、本発明のゴム系接着剤組成物は通常の保温温度
以下ではゲル化せず、その組成物の寿命が長い。Further, the rubber-based adhesive composition of the present invention does not gel at a temperature lower than a normal heat retention temperature, and the composition has a long life.
さらに、本発明の接着剤組成物はその製造に際して、
被接着体ゴムの未加硫ゴムを使用すれば簡単な操作で製
造することができる。Furthermore, the adhesive composition of the present invention, in its production,
If unvulcanized rubber as the adherend rubber is used, it can be manufactured by a simple operation.
第１図は、接着剤組成物を使用したゴム系被接着体の接
着方法を表わす説明図である。 第２図は、接着剤組成物中の有機ポリサルファイド化合
物の含有量と接着力との関係を表わすグラフである。 符号の説明 １……加硫ゴム、 ２……接着剤組成物、 ３……未加硫ゴムFIG. 1 is an explanatory view showing a method for adhering a rubber-based adherend using an adhesive composition. FIG. 2 is a graph showing the relationship between the content of the organic polysulfide compound in the adhesive composition and the adhesive strength. Explanation of symbols 1 ... Vulcanized rubber, 2 ... Adhesive composition, 3 ... Unvulcanized rubber
Claims (3)
コキシシラン基である有機ポリサルファイド化合物、及
び溶剤を含有してなるゴム系接着剤組成物。1. A rubber-based adhesive composition comprising a rubber, an organic polysulfide compound in which at least one terminal of the molecule is an alkoxysilane group, and a solvent.
る特許請求の範囲第１項に記載のゴム系接着剤組成物。2. The rubber-based adhesive composition according to claim 1, wherein the rubber is of the same quality as the rubber to be adhered.
とも一つの末端のアルコキシシラン基がトリメトキシシ
ラン基またはトリエトキシシラン基である特許請求の範
囲第１項に記載のゴム系接着剤組成物。3. The rubber-based adhesive composition according to claim 1, wherein at least one terminal alkoxysilane group of the organic polysulfide compound is a trimethoxysilane group or a triethoxysilane group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28633887A JPH086076B2 (en) | 1987-11-12 | 1987-11-12 | Rubber adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28633887A JPH086076B2 (en) | 1987-11-12 | 1987-11-12 | Rubber adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01129082A JPH01129082A (en) | 1989-05-22 |
| JPH086076B2 true JPH086076B2 (en) | 1996-01-24 |
Family
ID=17703093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28633887A Expired - Fee Related JPH086076B2 (en) | 1987-11-12 | 1987-11-12 | Rubber adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH086076B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268231A (en) * | 2011-05-25 | 2011-12-07 | 泰州市五行高分子材料科技有限公司 | Adhesive for hydrogenated butyronitrile aramid composite material, its preparation method and application method thereof |
-
1987
- 1987-11-12 JP JP28633887A patent/JPH086076B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01129082A (en) | 1989-05-22 |
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