JPH0129212B2 - - Google Patents
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- Publication number
- JPH0129212B2 JPH0129212B2 JP17331782A JP17331782A JPH0129212B2 JP H0129212 B2 JPH0129212 B2 JP H0129212B2 JP 17331782 A JP17331782 A JP 17331782A JP 17331782 A JP17331782 A JP 17331782A JP H0129212 B2 JPH0129212 B2 JP H0129212B2
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking
- rubber
- peroxide
- present
- transparency
- 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
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はイソプレン系ゴムの架橋（加硫）方法
に関する。詳しくは、透明性及び強度、特に引き
裂き強度に優れるイソプレン系ゴムの架橋方法で
ある。
天然ゴム及び合成ゴムのうち、
The present invention relates to a method for crosslinking (vulcanization) of isoprene rubber. Specifically, it is a method for crosslinking isoprene rubber that has excellent transparency and strength, particularly tear strength. Among natural rubber and synthetic rubber,
【式】の化学構造単位を有するゴ
ム（これらを総称してイソプレン系ゴムという）
は、タイヤ、はきものをはじめ各種工業用のゴム
製品として広く用いられている。上記ゴムは前述
の各種用途に適するように、各種の添加剤、ポリ
マー等をブレンドした後、架橋されるがこの際の
架橋方法の一つとして有機過酸化物による方法が
行われる。該方法によれば、一般に耐老化性のよ
い加硫ゴムが得られるが、非ゴム成分を含有する
ものの架橋や他のポリマーをブレンドしたものを
架橋する際には、架橋速度の遅れ等を生じるため
架橋促進剤や活性助剤等の助剤及び（又は）共架
橋剤が用いられる。
他方、ゴムの用途は多種多様であり透明性のよ
いもの、強度の大きいものなどに対する需要は大
きい。
そこで本発明は一つには高強度、特に高引き裂
き強度をまた別に高い透明性を、更にはこれらの
両性質を兼ね備えたゴムを提供する。
即ち、本発明はイソプレン系ゴムを過酸化物の
存在下で架橋させるに際し、強度及び（又は）透
明性を改良する架橋方法であつて、特定の共架橋
剤を併用することにより上記問題を解決するもの
である。
本発明はイソプレン系ゴムを過酸化物架橋させ
るに際し、共架橋剤としてビスアリルカーボネー
ト類を用いることを特徴とするイソプレン系ゴム
の架橋方法である。
本発明に用いるイソプレン系ゴムは
Rubber having the chemical structural unit of [formula] (these are collectively referred to as isoprene rubber)
is widely used as a rubber product for various industrial uses, including tires and footwear. The above-mentioned rubber is crosslinked after blending various additives, polymers, etc. in order to be suitable for the various uses mentioned above, and one of the crosslinking methods at this time is a method using an organic peroxide. According to this method, a vulcanized rubber with good aging resistance is generally obtained, but when crosslinking a material containing a non-rubber component or a material blended with other polymers, the crosslinking speed is delayed, etc. Therefore, auxiliary agents such as crosslinking accelerators and active auxiliaries and/or co-crosslinking agents are used. On the other hand, rubber has a wide variety of uses, and there is a great demand for rubber with good transparency and high strength. Accordingly, the present invention provides a rubber that has, on the one hand, high strength, especially high tear strength, and on the other hand, high transparency, and furthermore, has both of these properties. That is, the present invention is a crosslinking method for improving the strength and/or transparency when crosslinking isoprene rubber in the presence of peroxide, and the above problems are solved by using a specific co-crosslinking agent. It is something to do. The present invention is a method for crosslinking isoprene rubber, characterized in that bisallyl carbonates are used as a co-crosslinking agent when crosslinking isoprene rubber with peroxide. The isoprene rubber used in the present invention is
【式】で表わされる化学構造式の
重合単位を有するものであれば、天然ゴム、合成
ゴム等全てのものが範中に入いる。又、上記構造
を有するゴムは単独で用いる場合と上記ゴムに他
のゴム、例えばエチレンプロピレンゴム、SBR、
NBRなどのゴム類や塩素化ポリエチレン、エチ
レン−酢酸ビニル共重合体の如き熱可塑性樹脂を
半量以下、特に20wt％程度以下ブレンドしたも
のであつてもよい。又同様に上記イソプレンと他
のモノマーとの共重合体であつても、イソプレン
ユニツトが50wt％以上存在すれば、本発明の適
用範囲に含まれる。一般に共重合可能な他のモノ
マーの例はスチレン、ブタジエン、ブテン−１、
アクリロニトリル、酢酸ビニルなどである。
本発明に用いるゴム（ゴム混合物を含む）も一
般に用いられるゴムと同様、その強度や耐候性の
増進の目的又は増量の目的で無機質の充填剤例え
ばカーボンブラツク、珪酸塩類、含水珪酸（ホワ
イトカーボン）、タルク、クレーなどを添加する
ことができる。この場合、添加する無機質の種
類、特に粒径や量によつて透明性は阻害される。
従つて本発明における最も顕著な効果、即ち透明
性を有し、且つ強度の優れたゴム成形体を得るた
めには通常無機質充填剤を用いないか或いは極め
て微粒の充填剤、一般に透明ゴム用充填剤として
知られているものを用いる必要がある。
本発明に用いられる過酸化物としては、一般に
過酸化水素（Ｈ−Ｏ−Ｏ−Ｈ）の１個又は２個の
水素原子をアルキル基、アシール基などで置換し
たものが用いられる。例えば１，１−ジ−ｔ−ブ
チルペルオキシ−３，３，５−トリメチルシクロ
ヘキサン、過酸化ジtertブチル、過酸化２，２ジ
（tertブチル）ブタン、過酸化ベンゾイル等があ
る。
本発明において最も重要なことは、上記過酸化
物により架橋させるに際し、共架橋剤としてビス
アリルカーボネート類を用いることである。
本発明のビスアリルカーボネート類とは、カー
ボネート基を介して両側にアリル基を有する化合
物の総称を言う。又、これらビスアリルカーボネ
ート類の予備重合体も同様に利用できる。共架橋
剤として特定の粘度を必要とする場合には、効果
的である。該ビスアリルカーボネート類としては
例えば下記構造を有するものがある。
（R1、R2はそれぞれＨ又はCH3 ｎ＝１〜４）
上記共架橋剤の製造等については、公知の方法
等に特に制限されるものではない。また該共架橋
の使用量もブレンド物の種類や過酸化物の種類に
より異なるが、一般にゴムに対して0.2〜7phrが
好ましく、0.5〜3.5phr用いることにより、上記
効果を顕著に発揮される。上記共架橋剤の効果の
作用機構については明確でない。
本発明における架橋方法は、公知の方法が全て
採用されるが、一般的には例えばイソプレンゴム
に他のゴム或いは（及び）熱可塑性樹脂等を混練
後、該混練物に共架橋剤、ステアリン酸、過酸化
物の順に添加混練して百度〜百数十度の温度で数
分乃至数拾分間架橋を行わせる方法が用いられ
る。この際の混練方法、混合順位、或いは架橋温
度、時間等も配合物や架橋剤の種類等により任意
に選定すればよい。
又、本発明においてはゴムの配合時、架橋時、
架橋後の夫々について必要に応じて架橋促進剤、
架橋促進助剤、活性剤、分散剤、架橋遅延剤、老
化防止剤、補強剤、充填剤、軟化剤、可塑剤、粘
着付与剤、着色剤等を用いることもできる。
以下、本発明を具体的に設明するために実施例
を示すが、本発明は以下の実施例に特に限定され
るものではない。
実施例 １
第１表Ａ、Ｂ欄に示すような配合物をそれぞれ
第２表の０〜４欄に示す共架橋剤、ステアリン
酸、過酸化物などをこの順で添加、混練後24時間
以上放置したのち、150℃×８分の架橋条件で架
橋成型させた。その後、16時間以上放置たものを
下記の試験方法により透明性及び各種強度を求め
た。その結果を第３、４表に、Ａ配合にあつては
Ａ−０、Ａ−１、……、Ｂ配合にあつてはＢ−
０、Ｂ−１、……と表記して示した。
混練方法：ASTM Ｄ 3182に準拠
試験方法：JIS Ｋ 6301に準拠All rubbers such as natural rubber and synthetic rubber fall within the range as long as they have a polymerized unit of the chemical structural formula represented by the following formula. In addition, the rubber having the above structure may be used alone or may be combined with other rubbers such as ethylene propylene rubber, SBR,
It may be a blend of rubbers such as NBR, thermoplastic resins such as chlorinated polyethylene, and ethylene-vinyl acetate copolymer in an amount of less than half, especially less than about 20 wt%. Similarly, copolymers of the above-mentioned isoprene and other monomers fall within the scope of the present invention as long as they contain 50 wt% or more of isoprene units. Examples of other commonly copolymerizable monomers are styrene, butadiene, butene-1,
Acrylonitrile, vinyl acetate, etc. The rubber used in the present invention (including rubber mixtures) is similar to commonly used rubbers, and includes inorganic fillers such as carbon black, silicates, and hydrated silicic acid (white carbon) to improve its strength and weather resistance, or to increase its weight. , talc, clay, etc. can be added. In this case, transparency is inhibited depending on the type of inorganic substance added, especially the particle size and amount.
Therefore, in order to obtain the most remarkable effect of the present invention, that is, to obtain a rubber molded product having transparency and excellent strength, usually no inorganic filler is used or very fine filler is used, generally a filler for transparent rubber. It is necessary to use a known agent. The peroxide used in the present invention is generally hydrogen peroxide (H-O-O-H) in which one or two hydrogen atoms are replaced with an alkyl group, an acyl group, or the like. Examples include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-tert-butyl peroxide, 2,2-di(tert-butyl)butane peroxide, and benzoyl peroxide. The most important thing in the present invention is to use bisallyl carbonates as a co-crosslinking agent when crosslinking with the above-mentioned peroxide. The bisallyl carbonates of the present invention are a general term for compounds having allyl groups on both sides via a carbonate group. Prepolymers of these bisallyl carbonates can also be used in the same manner. It is effective when a specific viscosity is required as a co-crosslinking agent. Examples of the bisallyl carbonates include those having the following structure. (R 1 and R 2 are each H or CH 3 n=1 to 4) The production of the above-mentioned co-crosslinking agent is not particularly limited to known methods. The amount of co-crosslinking used also varies depending on the type of blend and the type of peroxide, but is generally preferably 0.2 to 7 phr relative to the rubber, and the above effects can be significantly exhibited by using 0.5 to 3.5 phr. The mechanism of action of the above-mentioned co-crosslinking agent is not clear. For the crosslinking method in the present invention, all known methods are adopted, but generally, for example, after kneading isoprene rubber with other rubber or (and) thermoplastic resin, the kneaded product is mixed with a co-crosslinking agent, stearic acid, etc. , peroxide are added and kneaded in this order, and crosslinking is carried out at a temperature of 100 to 100-odd degrees for several minutes to several tens of minutes. The kneading method, mixing order, crosslinking temperature, time, etc. at this time may be arbitrarily selected depending on the type of compound and crosslinking agent. In addition, in the present invention, at the time of compounding the rubber, at the time of crosslinking,
After crosslinking, add a crosslinking accelerator as necessary,
Crosslinking accelerators, activators, dispersants, crosslinking retarders, antiaging agents, reinforcing agents, fillers, softeners, plasticizers, tackifiers, colorants, etc. can also be used. EXAMPLES Hereinafter, examples will be shown to specifically establish the present invention, but the present invention is not particularly limited to the following examples. Example 1 A co-crosslinking agent, stearic acid, peroxide, etc. shown in columns 0 to 4 of Table 2 were added in this order to the formulation shown in columns A and B of Table 1, and kneaded for 24 hours or more. After being left to stand, it was crosslinked and molded under crosslinking conditions of 150°C for 8 minutes. Thereafter, after being left for 16 hours or more, transparency and various strengths were determined using the following test methods. The results are shown in Tables 3 and 4. For A combination, A-0, A-1, ..., for B combination, B-
They are expressed as 0, B-1, . . . . Kneading method: Conforms to ASTM D 3182 Test method: Conforms to JIS K 6301
【表】【table】
【表】【table】
【表】【table】
【表】
○×可 ×不可
[Table] ○× Possible × Not possible
【表】
透明感〓◎優 ○良 △やや可
○×可 ×不可
[Table] Transparency〓◎Excellent ○Good △Slightly OK ○× OK ×Not possible
Claims (1)
し、共架橋剤としてビスアリルカーボネート類を
用いることを特徴とするイソプレン系ゴムの架橋
方法。 ２ ビスアリルカーボネート類がゴムに対して
0.2〜7phrとなるように用いる特許請求の範囲第
１項記載の方法。 ３ ビスアリルカーボネート類がゴムに対して
0.5〜3.5phr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 crosslinking isoprene rubber, which comprises using bisallyl carbonates as a co-crosslinking agent when crosslinking isoprene rubber with peroxide. 2 Bisallyl carbonates against rubber
The method according to claim 1, which is used so that the amount of water is 0.2 to 7 phr. 3 Bisallyl carbonates against rubber
The method according to claim 1, wherein the amount is 0.5 to 3.5 phr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17331782A JPS5962652A (en) | 1982-10-04 | 1982-10-04 | Crosslinking method for isoprene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17331782A JPS5962652A (en) | 1982-10-04 | 1982-10-04 | Crosslinking method for isoprene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5962652A JPS5962652A (en) | 1984-04-10 |
| JPH0129212B2 true JPH0129212B2 (en) | 1989-06-08 |
Family
ID=15958190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17331782A Granted JPS5962652A (en) | 1982-10-04 | 1982-10-04 | Crosslinking method for isoprene rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5962652A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984939A (en) * | 1982-11-08 | 1984-05-16 | Tokuyama Soda Co Ltd | Rubber crosslinking method |
| US7335807B2 (en) * | 2001-12-21 | 2008-02-26 | Freudenberg-Nok General Partnership | Solventless liquid isoprene compounds |
-
1982
- 1982-10-04 JP JP17331782A patent/JPS5962652A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5962652A (en) | 1984-04-10 |
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