JPH0150334B2 - - Google Patents
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- Publication number
- JPH0150334B2 JPH0150334B2 JP57194619A JP19461982A JPH0150334B2 JP H0150334 B2 JPH0150334 B2 JP H0150334B2 JP 57194619 A JP57194619 A JP 57194619A JP 19461982 A JP19461982 A JP 19461982A JP H0150334 B2 JPH0150334 B2 JP H0150334B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- crosslinking
- 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
れるゴムの架橋方法である。
各種の天然ゴム及び合成ゴムは、タイヤ、はき
ものをはじめ各種工業用のゴム製品、家庭用品、
医療用品など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
る方法が行なわれる。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
ことを特徴とするゴムの架橋方法である。
本発明に用いるゴムは、例えばSBR（スチレ
ン・ブタジエンゴム），BR（ブタジエンゴム），
IR（イソプレンゴム），CR（クロロプレンゴム），
IIR（イソブチレン・イソプレンゴム），NBR（ア
クリロニトリル・ブタジエンゴム），EPM（エチ
レン・プロピレンゴム），EPDM（エチレン・プ
ロピレン・ジエンゴム）等、天然ゴム、合成ゴム
等全てのものが範ちゆうに入る。中でもSBR，
BR，NBR等のジエン系ゴムは本発明の効果が優
れるため好ましく、また単位モノマーが
The present invention relates to a method for crosslinking (vulcanization) of rubber. Specifically, it is a method for crosslinking rubber that has excellent transparency and strength, especially tear strength. Various natural and synthetic rubbers are used in tires, footwear, various industrial rubber products, household goods,
It is widely used as medical supplies. The above-mentioned rubber is crosslinked after blending with 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 high strength, particularly high tear strength, and 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 rubber in the presence of peroxide, and solves the above problems by using a specific co-crosslinking agent. It is. The present invention is a rubber crosslinking method characterized by using bisallyl carbonates as a co-crosslinking agent when peroxide crosslinking rubber. Rubbers used in the present invention include, for example, SBR (styrene-butadiene rubber), BR (butadiene rubber),
IR (isoprene rubber), CR (chloroprene rubber),
All rubbers such as natural rubber and synthetic rubber fall into this category, such as IIR (isobutylene/isoprene rubber), NBR (acrylonitrile/butadiene rubber), EPM (ethylene/propylene rubber), and EPDM (ethylene/propylene/diene rubber). Among them, SBR,
Diene rubbers such as BR and NBR are preferable because they have excellent effects in the present invention, and
【式】で表わされるイソプレン系
ゴムは特に好ましい。上記ゴムは単独で用いる場
合と、単一ゴムに他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％以下ブレンドし
たものであつてもよいし、又、上記モノマーの共
重合体であつてもよい。
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、一般的には例えばゴムに他のゴム
或は（及び）熱可塑性樹脂等を混練後、該混練物
に共架橋剤、過酸化物などを素練しつつ添加混練
するか或いは、前記充填剤、その他の添加剤に共
架橋剤及び（又は）過酸化物をあらかじめ混合し
た後、これをゴムに添加しつつ素練し均一に混練
した後、例えば百度〜百数十度の温度で数分乃至
数拾分間架橋反応を行わせる方法などが用いられ
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。
また、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、本発明を具体的に説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時間以上放置したもの
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
尚、第３〜８表において透明感の評価は◎：
優、〇：良、：可、△：やや可、×：不可と表
示する。Isoprene rubber represented by the formula is particularly preferred. The above rubber may be used alone, or may be a single rubber blended with other rubbers or thermoplastic resins such as chlorinated polyethylene or ethylene-vinyl acetate copolymer in an amount of less than half, especially less than 20 wt%. However, it may also be a copolymer of the above monomers. 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 to be used also varies depending on the type of blend and the type of peroxide, but is generally preferably from 0.2 to 7 phr relative to the rubber, and by using 0.5 to 3.5 phr, the above effects can be significantly exhibited. 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 the rubber with another rubber or (and) a thermoplastic resin, etc., the kneaded product is mixed with a co-crosslinking agent, peroxide, etc. Addition and kneading may be carried out while masticating the rubber, or after pre-mixing the co-crosslinking agent and/or peroxide with the filler and other additives, this may be added to the rubber and masticated uniformly. After kneading, a method is used in which a crosslinking reaction is carried out for several minutes to several tens of minutes at a temperature of, for example, 100 to 100-odd degrees. 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, crosslinking accelerators, crosslinking accelerators, activators, dispersants, crosslinking retarders, anti-aging agents, reinforcing agents, fillers, etc. are added as necessary during compounding of the rubber, during crosslinking, and after crosslinking. Agents, softeners, plasticizers, tackifiers, colorants, etc. can also be used. EXAMPLES Hereinafter, examples will be shown to specifically explain 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 In Tables 3 to 8, the evaluation of transparency is ◎:
Excellent, 〇: Good,: Fair, △: Fair, ×: Poor.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ２
実施例１の第１表Ａ欄のイソプレンゴムにかえ
て、SBR（Ｃ配合），CR（Ｄ配合），BR（Ｅ配合），
EPDM（Ｆ配合）を夫々用いた他は、全て実施例
１と同様な方法により透明性及び各種強度を求め
た。その結果を第５〜８表に示した。[Table] Example 2 Instead of isoprene rubber in column A of Table 1 of Example 1, SBR (C blend), CR (D blend), BR (E blend),
Transparency and various strengths were determined in the same manner as in Example 1, except that EPDM (F formulation) was used in each case. The results are shown in Tables 5-8.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
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。 ４ ゴムがジエン系のゴムである特許請求の範囲
第１項記載の方法。 ５ ゴムがイソプレン系ゴム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 rubber, which comprises using bisallyl carbonates as a co-crosslinking agent when crosslinking 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. 4. The method according to claim 1, wherein the rubber is a diene rubber. 5. The method according to claim 1, wherein the rubber is an isoprene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19461982A JPS5984939A (en) | 1982-11-08 | 1982-11-08 | Rubber crosslinking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19461982A JPS5984939A (en) | 1982-11-08 | 1982-11-08 | Rubber crosslinking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5984939A JPS5984939A (en) | 1984-05-16 |
| JPH0150334B2 true JPH0150334B2 (en) | 1989-10-30 |
Family
ID=16327540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19461982A Granted JPS5984939A (en) | 1982-11-08 | 1982-11-08 | Rubber crosslinking method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5984939A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5962652A (en) * | 1982-10-04 | 1984-04-10 | Tokuyama Soda Co Ltd | Crosslinking method for isoprene rubber |
-
1982
- 1982-11-08 JP JP19461982A patent/JPS5984939A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5984939A (en) | 1984-05-16 |
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