JPH0781035B2 - Chloroprene rubber compound - Google Patents
Chloroprene rubber compoundInfo
- Publication number
- JPH0781035B2 JPH0781035B2 JP61152332A JP15233286A JPH0781035B2 JP H0781035 B2 JPH0781035 B2 JP H0781035B2 JP 61152332 A JP61152332 A JP 61152332A JP 15233286 A JP15233286 A JP 15233286A JP H0781035 B2 JPH0781035 B2 JP H0781035B2
- Authority
- JP
- Japan
- Prior art keywords
- vulcanization
- chloroprene rubber
- time
- rubber
- rubber 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims description 8
- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 39
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 10
- 229960002447 thiram Drugs 0.000 claims description 10
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical group S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 9
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical class ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、加硫系がZnO/MgO/加硫促進剤である非イオウ
変性クロロプレンゴム（以下「CR」）の配合物に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a blend of a non-sulfur-modified chloroprene rubber (hereinafter “CR”) whose vulcanization system is ZnO / MgO / vulcanization accelerator.
＜従来の技術＞ 非イオウ変性のCRは、ZnO/MgOだけでは加硫が十分進行
しないため、イミダゾリン系の加硫促進剤、例えば２−
メルカプトイミダゾリン（エチレンチオウレア）を加え
たZnO/MgO/加硫促進剤（イミダゾリン系）の加硫系とし
ている。<Prior Art> Non-sulfur-modified CR does not undergo sufficient vulcanization only with ZnO / MgO, and therefore imidazoline-based vulcanization accelerators such as 2-
It is a vulcanization system of ZnO / MgO / vulcanization accelerator (imidazoline type) to which mercaptoimidazoline (ethylenethiourea) is added.
＜発明が解決しようとする問題点＞ しかし、上記加硫系では加硫曲線が、ジエン系ゴムにお
けるようなシヤープな山形曲線形ではなく、なだらかな
平坦曲線形であり、加硫速度が遅く、加硫時間が長くな
る傾向にあつた。例えば160℃で型加硫を行なつた場
合、十分な加硫を行なうためには12分以上の加硫時間を
要した。なお、型温、即ち加硫温度を上昇させれば、加
硫時間は短縮できるが、ゴム材料セツト時の金型接触部
にスコーチが発したり離型時に引き裂け等が発生するお
それがあつた。<Problems to be Solved by the Invention> However, in the above-mentioned vulcanization system, the vulcanization curve is not a sharp mountain curve shape like in diene rubber, but a smooth flat curve shape, and the vulcanization rate is slow, The vulcanization time tended to be long. For example, when mold vulcanization was performed at 160 ° C., vulcanization time of 12 minutes or more was required for sufficient vulcanization. Although the vulcanization time can be shortened by increasing the mold temperature, that is, the vulcanization temperature, there is a possibility that a scorch may be generated at the mold contact portion at the time of setting the rubber material, or tearing may occur at the time of releasing the mold.
＜問題点を解決するための手段＞ 本発明者らは、上記問題点を解決するために、鋭意開発
に努力した結果、下記構成のCR配合物に想到し得た。<Means for Solving the Problems> The inventors of the present invention have come up with a CR composition having the following constitution as a result of intensive efforts for development in order to solve the above problems.
加硫系がZnO/MgO/加硫促進剤である非イオウ変性クロロ
プレンゴムの配合物において、加硫促進剤が、イミダゾ
リン系，チオウレア系，チウラム系の三成分混合物であ
ることを特徴とする。A compound of a non-sulfur-modified chloroprene rubber in which the vulcanization system is ZnO / MgO / vulcanization accelerator is characterized in that the vulcanization accelerator is a ternary mixture of an imidazoline type, a thiourea type, and a thiuram type.
＜構成の詳細な説明＞ 以下、本発明の構成について詳細に説明をする。<Detailed Description of Configuration> The configuration of the present invention will be described in detail below.
本発明に使用するポリマーは、非イオウ変性型（Ｗ型）
のCRを用いる。具体的には、昭和ネオプレン（株）から
製造販売されているネオプレンＷ・WM−１・WHV、WB、W
RT、WX−Ｊ等を挙げることができる。The polymer used in the present invention is a non-sulfur modified type (W type)
Use CR. Specifically, Neoprene W ・ WM-1 ・ WHV, WB, W manufactured and sold by Showa Neoprene Co., Ltd.
RT, WX-J, etc. can be mentioned.
そして、ZnO/MgO/加硫促進剤の加硫系において、加硫促
進剤を、２−メルカプトイミダゾリン、トリメチルチオ
ウレア、テトラメチルチウラムジスルフィドの三成分併
用型とする。Then, in the vulcanization system of ZnO / MgO / vulcanization accelerator, the vulcanization accelerator is a three-component combination type of 2-mercaptoimidazoline, trimethylthiourea, and tetramethylthiuram disulfide.
上記加硫系における配合量は、通常、ZnO/MgO＝5phr/4p
hrとし、２−メルカプトイミダゾリン0.1〜1.0phr（望
ましくは0.2〜0.5phr），トリメチルチオウレア0.5〜2.
0phr（望ましくは1.3〜1.7phr），テトラメチルチウラ
ムジスルフィド0.1〜1.0phr（望ましくは0.3〜0.7phr）
とする。The compounding amount in the above vulcanization system is usually ZnO / MgO = 5phr / 4p
hr, 2-mercaptoimidazoline 0.1-1.0 phr (preferably 0.2-0.5 phr), trimethylthiourea 0.5-2.
0 phr (desirably 1.3 to 1.7 phr), tetramethylthiuram disulfide 0.1 to 1.0 phr (desirably 0.3 to 0.7 phr)
And
そして、本発明のゴム配合物には、上記加硫系副資材の
他に、通常CR配合物に配合されるカーボンブラツク，老
化防止剤，白色充填剤，軟化剤，滑剤等が配合される。In addition to the above-mentioned vulcanization-based auxiliary material, the rubber compound of the present invention contains carbon black, an antioxidant, a white filler, a softening agent, a lubricant, etc. which are usually compounded in a CR compound.
このゴム配合物の混練は、一般に行なわれている如く、
ロール，バンバリーミキサー等によつて行なう。また、
ゴム配合物の加硫も、通常の条件・設備で行なえる。Kneading of this rubber compound, as is generally done,
Use a roll, Banbury mixer, etc. Also,
Vulcanization of rubber compounds can also be performed under normal conditions and equipment.
＜発明の作用・効果＞ 本発明のCR配合物は、ZnO/MgO/加硫促進剤の加硫系にお
いて、加硫促進剤を２−メルカプトイミダゾリン、トリ
メチルチオウレア、テトラメチルチウラムジスルフィド
の三成分併用型のものとすることにより、加工性に問題
（混練時のゴムヤケ等）を発生させずに、しかも物性的
にも優れたゴム加硫物を、従来に比して短かい加硫時間
で得ることができる。<Operations and effects of the invention> In the vulcanization system of ZnO / MgO / vulcanization accelerator, the CR composition of the present invention is a combination of three components of 2-mercaptoimidazoline, trimethylthiourea, and tetramethylthiuram disulfide. By using a mold, a rubber vulcanizate that does not cause problems in processability (rubber burns during kneading, etc.) and has excellent physical properties can be obtained in a shorter vulcanization time than before. be able to.
＜実施例＞ 本発明の効果を確認するために行なつた、実施例につい
て比較例とともに説明をする。<Examples> Examples performed to confirm the effects of the present invention will be described together with comparative examples.
別記基本配合処方において、加硫促進剤を第１表に示す
如く組合せた組成の各実施例（比較例）のゴム配合物を
混練した後のゴム材料について、下記方法により各試験
を行なつた。Each test was carried out by the following method on the rubber material after kneading the rubber compound of each Example (Comparative Example) having a composition in which the vulcanization accelerator was combined as shown in Table 1 in the separately mentioned basic compounding formulation. .
（１）加硫速度 JSRキユラストメーターIV型（製造；今中機械工業
（株），販売；日合商事（株））を用いて加硫速度を下
記条件でで判定した。尚、キユラストメータは、一定温
度で加硫又は硬化中の試料に一定振幅の振動変形を与え
て発生する応力を連続的に測定するものである。(1) Vulcanization rate The vulcanization rate was determined under the following conditions using a JSR Kyulastometer IV type (manufactured by Imanaka Machinery Co., Ltd., sold by Higo Shoji Co., Ltd.). The kyulast meter continuously measures the stress generated by subjecting a sample being vulcanized or cured at a constant temperature to a vibration deformation of a constant amplitude.
測定条件：振幅角度±３゜，振動数100cpm,170℃で得ら
れた応力の連続曲線において、最大応力に対しその90％
に達する時間をT90（分）、10％に達する時間をT
10（分）とした。この場合、T90に相当する時間がその
ゴム試料の試験温度における適正加硫時間、またT10に
相当する時間がスコーチタイムとなる。Measurement conditions: 90% of the maximum stress in a continuous curve of stress obtained at an amplitude angle of ± 3 °, a frequency of 100 cpm and 170 ° C.
Time to reach T 90 (min), Time to reach 10% T
It was set to 10 (minutes). In this case, the time corresponding to T 90 is the proper vulcanization time at the test temperature of the rubber sample, and the time corresponding to T 10 is the scorch time.
（２）常態物性 各ゴム材料から（170℃×T90;プレス加硫）によりシー
ト（2mmt）を得、JISK6301に準じて、硬さ（HS），引張
強さ（TB），伸び（EB）を求めた。(2) Normal physical properties Sheets (2 mmt) were obtained from each rubber material (170 ° C × T 90 ; press vulcanization), and hardness (H S ), tensile strength (T B ), elongation (according to JIS K6301) E B ).
第１表に示す試験結果から、下記のことがわかる。The test results shown in Table 1 show the following.
２−メルカプトイミダゾリン（＃22）とテトラメチル
チウラムジスルフィド（TT）との組合せではT90が長
く、加硫時間の短縮が望めない（比較例１参照）。な
お、チウラム系を多くするとT90が長くなる。The combination of 2-mercaptoimidazoline (# 22) and tetramethylthiuram disulfide (TT) has a long T 90 and cannot be expected to shorten the vulcanization time (see Comparative Example 1). In addition, T 90 becomes longer when the thiuram system is increased.
２−メルカプトイミダゾリンとトリメチルチオウレア
（TMU）の組合せでは、T90が短かくなり、加硫時間の短
縮が可能であるが、T10も短かくなり、混練時のヤケ
（スコーチ）が発生しやすく、加工性に問題を生じる
（比較例２参照）。With a combination of 2-mercaptoimidazoline and trimethylthiourea (TMU), T 90 becomes short and vulcanization time can be shortened, but T 10 also becomes short and burns (scorch) at the time of kneading easily occur. However, there is a problem in workability (see Comparative Example 2).
トリメチルチオウレアとテトラメチルチオウラムジス
ルフィドの組合せでは、T90が短かく、かつT10が長くな
り、加硫特性的に問題はないが、ゴム架橋密度が十分で
なく（HS低下、EB大）、加硫品物性に問題を生じる（比
較例３参照）。The combination of trimethyl thiourea and tetramethyl thiourea Ulam disulfide, T 90 is short, and T 10 is increased, there is no problem in vulcanization characteristics, the rubber crosslink density is not sufficient (H S decreases, E B Univ.) However, problems occur in the physical properties of the vulcanized product (see Comparative Example 3).
トリメチルチオウレア,2−メルカプトイミダゾリン，
テトラメチルチウラムジスルフィドの三成分を組合せた
各実施例の場合は、T90が短かく、かつT10も比較的長
く、しかも加硫品物性も良好である。特に、チウラム系
を多くした場合は、T10をほとんど短かくせずに、T90を
短かくでき望ましい（実施例２・３参照）。Trimethylthiourea, 2-mercaptoimidazoline,
In the case of each example in which the three components of tetramethylthiuram disulfide are combined, T 90 is short, T 10 is relatively long, and the physical properties of the vulcanized product are good. In particular, when increasing the thiuram, the T 10 with little short, desirably it is shorter the T 90 (see Example 2, 3).
＜基本配合処方＞ ポリマー（ネオプレンWRT※） 100重量部 カーボンブラツク（FEF） 40 ZnO ５ MgO ４ 白色充填剤 20 軟化剤（可塑剤） 20 老化防止剤 ６ 加硫促進剤（表示） 変量 ※昭和電光・デユポン（株）製。<Basic compounding recipe> Polymer (Neoprene WRT * ) 100 parts by weight Carbon black (FEF) 40 ZnO 5 MgO 4 White filler 20 Softener (plasticizer) 20 Anti-aging agent 6 Vulcanization accelerator (display) Variable * Showa Denkou・ Manufactured by Deupon Co., Ltd.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯島 賢治 東京都江東区木場３−10−７−604 (56)参考文献 特開 昭53−26847（ＪＰ，Ａ) 特開 昭60−86137（ＪＰ，Ａ) 特開 昭59−227946（ＪＰ，Ａ) 特開 昭59−227947（ＪＰ，Ａ) ─────────────────────────────────────────────────── --- Continued from the front page (72) Inventor Kenji Iijima 3-10-7-604 Kiba, Koto-ku, Tokyo (56) References JP-A-53-26847 (JP, A) JP-A-60-86137 (JP , A) JP 59-227946 (JP, A) JP 59-227947 (JP, A)
Claims (1)
ウ変性クロロプレンゴムの配合物において、 前記加硫促進剤が、２−メルカプトイミダゾリン、トリ
メチルチオウレア、テトラメチルチウラムジスルフィド
の三成分併用型であること、 を特徴とするクロロプレンゴム配合物。1. A blend of non-sulfur-modified chloroprene rubber whose vulcanization system is ZnO / MgO / vulcanization accelerator, wherein the vulcanization accelerator is 2-mercaptoimidazoline, trimethylthiourea, or tetramethylthiuram disulfide. A chloroprene rubber compound characterized by being a combination of components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61152332A JPH0781035B2 (en) | 1986-06-27 | 1986-06-27 | Chloroprene rubber compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61152332A JPH0781035B2 (en) | 1986-06-27 | 1986-06-27 | Chloroprene rubber compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS638440A JPS638440A (en) | 1988-01-14 |
| JPH0781035B2 true JPH0781035B2 (en) | 1995-08-30 |
Family
ID=15538219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61152332A Expired - Lifetime JPH0781035B2 (en) | 1986-06-27 | 1986-06-27 | Chloroprene rubber compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0781035B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641538B2 (en) * | 1988-04-20 | 1994-06-01 | 豊田合成株式会社 | Chloroprene rubber compound |
| CN1922696B (en) | 2004-03-09 | 2010-05-26 | 大日本印刷株式会社 | Electron beam irradiation device |
| JP4641844B2 (en) | 2005-03-25 | 2011-03-02 | 大日本印刷株式会社 | Electron beam irradiation device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5326847A (en) * | 1976-08-25 | 1978-03-13 | Dainichi Nippon Cables Ltd | Vulcanizable chloroprene rubber compositions for rubber belts |
| JPS6054977B2 (en) * | 1983-06-09 | 1985-12-03 | 大阪曹達株式会社 | Halogen-containing polymer vulcanization composition |
| JPS6054976B2 (en) * | 1983-06-09 | 1985-12-03 | 大阪曹達株式会社 | Halogen-containing polymer vulcanization composition |
| JPS6086137A (en) * | 1983-10-19 | 1985-05-15 | Hitachi Cable Ltd | Chloroprene rubber composition |
-
1986
- 1986-06-27 JP JP61152332A patent/JPH0781035B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS638440A (en) | 1988-01-14 |
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