JPH0641538B2 - Chloroprene rubber compound - Google Patents
Chloroprene rubber compoundInfo
- Publication number
- JPH0641538B2 JPH0641538B2 JP63097881A JP9788188A JPH0641538B2 JP H0641538 B2 JPH0641538 B2 JP H0641538B2 JP 63097881 A JP63097881 A JP 63097881A JP 9788188 A JP9788188 A JP 9788188A JP H0641538 B2 JPH0641538 B2 JP H0641538B2
- Authority
- JP
- Japan
- Prior art keywords
- vulcanization
- type
- chloroprene rubber
- rubber
- imidazoline
- 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
- Processes Of Treating Macromolecular Substances (AREA)
- 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、一般に、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> In general, non-sulfur-modified CR does not undergo sufficient vulcanization with ZnO / MgO alone, so an imidazoline-based vulcanization accelerator,
For example, a vulcanization system of ZnO / MgO / vulcanization accelerator (imidazoline type) to which 2-mercaptoimidazoline (ethylenethiourea) is added is used.
＜発明が解決しようとする課題＞ 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して、アンダカツトを有する成
形品のような場合、離型時に成形品に破れ（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 as in diene rubber, but a smooth flat curve shape, and the vulcanization rate is slow and Sulfurization time tends to be long. For example, when mold vulcanization was performed at 160 ° C., vulcanization time of 12 minutes or more was required to perform sufficient vulcanization. If the mold temperature, that is, the vulcanization temperature is increased,
Although the vulcanization time can be shortened, when a rubber material is set, a scorch is generated at the mold contact part, and in the case of a molded product with an undercut, the molded product is torn (teared) when released.
Etc. may occur.
これらの問題点を解決するため、特開昭６３−８４４０
号公報において、下記構成のＣＲ配合物が提案されてい
る。In order to solve these problems, JP-A-63-8440
In the publication, a CR compound having the following constitution is proposed.
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併用型であ
ることを特徴とする。In a blend of non-sulfur-modified chloroprene rubber in which the vulcanization system is ZnO / MgO / vulcanization accelerator, the vulcanization accelerator is a combination of imidazoline-based, thiourea-based, and thiuram-based three-component type .
＜発明が解決しようとする課題＞ この加硫系の場合、本発明者らが種々検討した結果、ス
コーチ時間（加硫曲線の立上り開始までの時間）が長
く、かつ立上りがシヤープで理想的な加硫曲線を示す
が、架橋密度（加硫度）が若干高目であり、加硫ゴムの
物性において、破断伸びの大きなものを得難いことが分
つた。<Problems to be Solved by the Invention> In the case of this vulcanization system, as a result of various studies by the present inventors, the scorch time (the time until the start of the vulcanization curve rise) is long and the rise is ideal. A vulcanization curve is shown, but it was found that the crosslink density (vulcanization degree) was slightly higher, and it was difficult to obtain a vulcanized rubber having a large elongation at break.
＜課題を解決するための手段＞ 本発明のＣＲ配合物は、加硫系がZnO/MgO/加硫促進剤で
ある非イオウ変性の配合物において、加硫促進剤を、イ
ミダゾリン系、チオウレア系、チアゾール系の三成分併
用型、又は、これら三成分にチウラム系を加えた四成分
併用型とすることにより上記課題を解決するものであ
る。<Means for Solving the Problems> The CR blend of the present invention is a non-sulfur-modified blend in which the vulcanization system is ZnO / MgO / vulcanization accelerator, and the vulcanization accelerator is imidazoline-based or thiourea-based. The above problem is solved by using a thiazole-based three-component combination type or a four-component combination type in which thiuram-type is added to these three components.
＜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。なお、
説明中、配合部数を示す「部」は、特にことわらない限
り「重量部」を意味する。<Detailed Description of Configuration> The configuration of the present invention will be described in detail below. In addition,
In the description, “part” indicating the number of parts to be mixed means “part by weight” unless otherwise specified.
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、昭和電工・デユポン
（株）から製造販売されているネオプレンＷ・ＷＭ−１
・ＷＨＶ、ＷＢ、ＷＲＴ、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)
CR is used. Specifically, Neoprene W / WM-1 manufactured and sold by Showa Denko Deupon Co., Ltd.
-WHV, WB, WRT, 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、下記イミダゾリン系、チオウレア系（イミ
ダゾリン系を除く）、チアゾール系の三成分併用型、
又は、これら三成分に下記チウラム系を加えた四成分
併用型とする。Then, in the vulcanization system of ZnO / MgO / vulcanization accelerator, the vulcanization accelerator is the following imidazoline-based, thiourea-based (excluding imidazoline-based), three-component combination type of thiazole,
Alternatively, a four-component combination type is prepared by adding the following thiuram system to these three components.
２−メルカプトイミダゾリン（以下「＃２２」）等。2-mercaptoimidazoline (hereinafter "# 22") and the like.
トリメチルチオウレア（以下「ＴＭＵ」）、チオカル
バニライド、1,3−ジエチルチオウレア、ジオルトトリ
ルチオウレア、ジブチルチオウレア、テトラメチルチオ
ウレア、ジメチルエチルチオウレア、ジラウリルチオウ
レア等。Trimethylthiourea (hereinafter "TMU"), thiocarbanilide, 1,3-diethylthiourea, diortotolylthiourea, dibutylthiourea, tetramethylthiourea, dimethylethylthiourea, dilaurylthiourea and the like.
ジベンゾチアジルジスルフイド（以下「ＤＭ」）、２
−メルカプトベンゾチアゾール（金属塩を含む。）、２
−ベンゾチアゾール等。Dibenzothiazyl disulphide (hereinafter "DM"), 2
-Mercaptobenzothiazole (including metal salt), 2
-Benzothiazole and the like.
テトラメチルチウラムジスルフイド（以下「Ｔ
Ｔ」）、テトラエチルチウラムジスルフイド、テトラブ
チルチウラムジスルフイド、テトラメチルチウラムモノ
スルフイド、ジペンタメチレンチウラムテトラスルフイ
ド等。Tetramethyl thiuram disulfide (hereinafter "T
T ”), tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram tetrasulfide and the like.
上記加硫系における配合量は、通常、ＣＰ１００部に対
しZnO/MgO＝５部／４部とし、イミダゾリン系（＃２２
の場合）0.1〜1.0部（望ましくは0.2〜0.5部）、チオウ
レア系（ＴＭＵの場合）0.5〜2.0部（望ましくは1.3〜
1.7部）、チアゾール系（ＤＭの場合）0.5〜2.0部（望
ましくは0.7〜1.3部），チウラム系（ＴＴの場合）0.1
〜1.0部（望ましくは0.3〜0.7部）とする。The compounding amount in the above-mentioned vulcanization system is usually ZnO / MgO = 5 parts / 4 parts to 100 parts of CP, and the imidazoline system (# 22
0.1 to 1.0 part (preferably 0.2 to 0.5 part), thiourea (in the case of TMU) 0.5 to 2.0 part (desirably 1.3 to)
1.7 parts), thiazole-based (DM) 0.5-2.0 parts (desirably 0.7-1.3 parts), thiuram-based (TT) 0.1
~ 1.0 part (desirably 0.3 to 0.7 part).
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。And, in the rubber composition of the present invention, in addition to the above-mentioned vulcanization-based auxiliary material, a carbon black usually compounded in a CR compound,
Anti-aging agents, white fillers, softeners, lubricants and the like are added.
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、加硫促進剤をイミダゾリン系、チオウレア系、
チアゾール系の三成分併用型、又は、これら三成分にチ
ラウム系を加えた四成分併用型のものとすることによ
り、加硫促進剤を特開昭６３−８４４０号公報に記載の
三成分併用型とした場合と同様、加工性に問題（混練時
のゴムヤケ等）を発生させずに、ゴム加硫物を短かい加
硫時間で得ることができるばかりでなく、後述の実施例
で示す如く、特に伸び物性（ＥB）の大きな加硫物を得
ることができる。この伸び物性は、四成分併用型の方が
三成分併用型に比して優れている。<Operations and effects of the invention> The CR compound of the present invention is a vulcanization system of ZnO / MgO / vulcanization accelerator, wherein the vulcanization accelerator is an imidazoline type, a thiourea type,
By using a thiazole-based three-component combination type or a four-component combination type obtained by adding a thirium-type to these three components, the vulcanization accelerator can be used as the three-component combination type described in JP-A-63-8440. In the same manner as the above, not only can the rubber vulcanizate be obtained in a short vulcanization time without causing problems in processability (rubber burn during kneading, etc.), but as shown in the examples described below, In particular, a vulcanized product having a large elongation property (E B ) can be obtained. The elongation property of the four-component combination type is superior to that of the three-component combination type.
従つて、アンダカツトの大きなゴム成形品に本発明のＣ
Ｒ配合物を使用した場合、従来に比して、離型時等に成
形品等に破れ等が発生し難い等の効果を奏する。Accordingly, the C of the present invention can be applied to a rubber molding having a large undercut.
When the R compound is used, there is an effect that the molded product or the like is less likely to be broken at the time of releasing from the mold, as compared with the conventional case.
＜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III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
記条件で判定した。なお、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 III 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Ｔ10（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時間となる。Measurement conditions: amplitude angle ± 3 °, frequency 100 cpm, 170
In the continuous curve of stress obtained at ° C, the time to reach 90% of the maximum stress was T 90 (minutes), and the time to reach 10% was T 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 各ゴム材料からプレス加硫（１７０℃×Ｔ90（分））に
よりテストピースを得、ＪＩＳＫ６３０１に準じて、硬
さ（ＨS）、引張強さ（ＴB）、伸び（ＥB）を求めた。(2) normal physical properties press vulcanization from each rubber material (170 ° C. × T 90 (min)) by obtain a test piece, in accordance with JIS K6301, hardness (H S), tensile strength (T B), elongation ( E B ).
第１表に示す試験結果から、下記のことが分る。The following can be seen from the test results shown in Table 1.
イミダゾリン系（＃２２）とチウラム系（ＴＴ）と
の、又は、イミダゾリン系（＃２２）とチアゾール系
（ＤＭ）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・２）。A combination of an imidazoline type (# 22) and a thiuram type (TT), or a combination of an imidazoline type (# 22) and a thiazole type (DM) has a long T 90 and cannot shorten the vulcanization time (Comparative Example 1・ 2).
チオウレア系とチウラム系の組合せでは、Ｔ90が短か
く、かつＴ10が長くなり、加硫速度的に問題はないが、
ゴムの架橋密度が十分でなく（ＨS低下、ＥB大）、加硫
ゴム物性に問題を生じる（比較例３）。In the combination of thiourea type and thiuram type, T 90 is short and T 10 is long, so there is no problem in vulcanization rate,
The cross-linking density of the rubber is not sufficient (reduction in H S , large E B ) and problems occur in the physical properties of the vulcanized rubber (Comparative Example 3).
イミダゾリン系、チオウレア系、チウラム系の三成分
を組合せた場合は、Ｔ90が短かく、かつＴ10も比較的長
く、しかも加硫ゴム物性もほぼ良好であるが、伸び（Ｅ
B）が実施例に比して小さい（比較例４）。When three components of imidazoline type, thiourea type and thiuram type are combined, T 90 is short, T 10 is relatively long, and the physical properties of the vulcanized rubber are almost good, but the elongation (E
B ) is smaller than that of the example (Comparative example 4).
イミダゾリン系、チオウレア系、チアゾール系の三成
分を組合せた、三成分併用型又は、それら三成分にチウ
ラム系を加えた四成分併用型の場合は、Ｔ90が短かく、
かつＴ10も従来例と同等であり、しかも加硫ゴム物性も
ほぼ良好であり、特に、伸び（ＥB）が比較例４に比し
て大きい。そして、四成分併用型の方が三成分併用型よ
り伸びが大きい（実施例１・２）。In the case of a three-component combination type combining three components of an imidazoline type, a thiourea type, and a thiazole type, or a four-component combination type in which thiuram type is added to these three components, T 90 is short,
Moreover, T 10 is also equal to that of the conventional example, and the physical properties of the vulcanized rubber are almost good, and in particular, the elongation (E B ) is larger than that of Comparative Example 4. Further, the four-component combination type has a larger elongation than the three-component combination type (Examples 1 and 2).
＜基本配合処方＞ ポリマー（ネオプレンＷＲＴ※１） １００重量部 カーボンブラック（ＦＥＦ） ６０ 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 ※１）昭和電工・デユポン（株）製。<Basic compounding recipe> Polymer (neoprene WRT * 1 ) 100 parts by weight Carbon black (FEF) 60 ZnO 5 MgO 4 White filler 20 Softener (plasticizer) 20 Anti-aging agent 6 Vulcanization accelerator (display) Variable amount * 1 ) Showa Denko Deupon Co., Ltd.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 秀典 愛知県西春日井郡春日村大字落合字長畑１ 番地 豊田合成株式会社内 (56)参考文献 特開 昭58−87139（ＪＰ，Ａ) 特開 昭63−8440（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hidenori Hayashi Inventor Hidenori Kasuga-mura, Aichi 1st Ochiai, Nagahata, Nagachibata Toyoda Gosei Co., Ltd. (56) Reference JP-A-58-87139 (JP, A) JP-A-SHO 63-8440 (JP, A)
Claims (2)
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、イミダゾリン系、チオウレア系、チ
アゾール系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 compound of non-sulfur-modified chloroprene rubber in which the vulcanization system is ZnO / MgO / vulcanization accelerator, wherein the vulcanization accelerator is a three-component combination type of imidazoline type, thiourea type and thiazole type. A chloroprene rubber compound characterized by being present.
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、イミダゾリン系、チオウレア系、チ
アゾール系、チウラム系の四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。2. A compound of non-sulfur-modified chloroprene rubber, wherein the vulcanization system is ZnO / MgO / vulcanization accelerator, wherein the vulcanization accelerator is an imidazoline-based, thiourea-based, thiazole-based or thiuram-based four-component compound. A chloroprene rubber compound characterized by being a combination type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63097881A JPH0641538B2 (en) | 1988-04-20 | 1988-04-20 | Chloroprene rubber compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63097881A JPH0641538B2 (en) | 1988-04-20 | 1988-04-20 | Chloroprene rubber compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01268737A JPH01268737A (en) | 1989-10-26 |
| JPH0641538B2 true JPH0641538B2 (en) | 1994-06-01 |
Family
ID=14204089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63097881A Expired - Lifetime JPH0641538B2 (en) | 1988-04-20 | 1988-04-20 | Chloroprene rubber compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0641538B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6105345B2 (en) * | 2013-03-21 | 2017-03-29 | 三菱電線工業株式会社 | Chloroprene rubber composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6048544B2 (en) * | 1978-08-21 | 1985-10-28 | 三菱電線工業株式会社 | Crosslinkable chlorine-containing elastomer composition |
| JPS5887139A (en) * | 1981-11-18 | 1983-05-24 | Mitsuboshi Belting Ltd | Rubber compounding composition |
| JPH0781035B2 (en) * | 1986-06-27 | 1995-08-30 | 豊田合成株式会社 | Chloroprene rubber compound |
-
1988
- 1988-04-20 JP JP63097881A patent/JPH0641538B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01268737A (en) | 1989-10-26 |
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