JPS6116294B2 - - Google Patents
Info
- Publication number
- JPS6116294B2 JPS6116294B2 JP56168305A JP16830581A JPS6116294B2 JP S6116294 B2 JPS6116294 B2 JP S6116294B2 JP 56168305 A JP56168305 A JP 56168305A JP 16830581 A JP16830581 A JP 16830581A JP S6116294 B2 JPS6116294 B2 JP S6116294B2
- Authority
- JP
- Japan
- Prior art keywords
- urethane rubber
- carbon black
- vulcanization
- vulcanized
- ester
- 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
Links
- 229920006311 Urethane elastomer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
〔産業上の利用分野〕
本発明は常圧加硫可能なウレタンゴム組成物に
関するものである。
〔従来の技術〕
ゴム組成物の加硫はゴムと加硫剤の架橋反応で
ある。この架橋反応では副生物が生じしかも加熱
によりゴム組成物中に抱き込まれた水分、混練空
気等が揮散する。通常、ゴムの加硫工程では架橋
反応副生物、水分、混練空気等の揮散による発泡
不良を防止するため、プレス加硫または加硫罐加
硫法が行われている。
さて、ゴム組成物の加硫において過酸化物加硫
は、過酸化物の分解反応が伴うため、発泡不良が
最も生じ易い。特に過酸化物加硫のエステル系ウ
レタンゴム組成物では過酸化物とエステル系ウレ
タンゴムとの架橋反応により副生物が多く生じる
ため、常圧加硫において発泡不良が避けられなか
つた。
このようなわけでエステル系ウレタンゴム組成
物による長尺あるいは大型の常圧加硫成形品を作
ることが困難であつた。
〔発明が解決しようとする問題点〕
本発明はかかる点に立つて為されたものであつ
て、前記した従来技術の欠点を解消し、常圧で加
硫しても発泡不良が生じない常圧加硫可能なウレ
タンゴム組成物を提供することにある。
〔問題点を解決するための手段〕
本発明の要旨とするところは、過酸化物および
導電性カーボンブラツクを配合して成るウレタン
ゴム組成物において、ウレタンゴムがエステル系
ウレタンゴムであつて、該エステル系ウレタンゴ
ム100重量部に対し、ASTM−D2414のによる
DBP吸油量が250ml／100g以上でかつ窒素吸着法
による表面積が500m2／ｇ以上である導電性カー
ボンブラツクを３〜18重量部配合して成ることを
特徴とする常圧加硫可能なウレタンゴム組成物に
ある。
本発明において、エステル系ウレタンゴムとは
ポリエステルオリゴマーとポリイソシアネートと
から得られるウレタンゴムであつて、工業的には
西独バイエル社よりウレパン640等が市販されて
いる。本発明においてウレタンゴムとしてエステ
ル系ウレタンゴムに限定したのは、エーテル系ウ
レタンゴムより耐摩耗性や耐薬品性を向上できる
ものの架橋反応副生物による発泡不良が多発しや
すいためである。
本発明において、極く普通のカーボンブラツ
ク、例えばフアーネスブラツク、サーマールブラ
ツク、チヤンネルブラツクあるいはアセチレンブ
ラツクを用いたものでは、これらの吸油量が250
ml／100g以下でかつ窒素着法測定の表面積が500
m2／ｇ以下と小さいため発泡を抑止できない。
これに対して本発明で用いる導電性カーボンブ
ラツクは発泡抑止効果がある吸油量が250ml／
100g以上でかつ表面積が500m2／ｇ以上の特殊な
ものであつて、従来ウレタンゴム等には配合され
た例がないものである。
本発明においてこの特殊な導電性カーボンブラ
ツクの配合量を３〜18重量部と限定したのは、３
重量部以下では発泡抑止効果がなく、18重量部以
上では配合量に比例した発泡抑止効果を発揮でき
ず、しかも特殊なカーボンブラツクであるため急
激な価格上昇を招くためである。
〔作用〕
本発明の作用は、エステル系ウレタンゴム100
重量部に対して、ASTM−D2414によるDBP吸油
量が250ml／100g以上でかつ窒素吸着法による表
面積500m2／ｇ以上である導電性カーボンブラツ
クを３〜18重量部配合することにより、エステル
系ウレタンゴムと過酸化物との架橋反応により副
生する多量の揮発成分を吸着し、その結果常圧で
加硫しても発泡を効果的に抑止することにある。
〔実施例〕
以下、本発明のウレタンゴム組成物をいくつか
の実施例により、更に具体的に説明する。
なお、これらの実施例および比較例で用いた配
合材料（配合欄における（ ）付きの番号）は下
記の通りである。
(1) ウレパン640（西独バイエル社製）
(2) ケツチエンブラツクEC（日本イーシー(株)
製）
DBP吸油量 350ml／100g
表面積（窒素吸着法） 950m2／ｇ
(3) シースト３（東海電極製カーボンブラツク
〔HAF〕）
DBP吸油量 102ml／100g
表面積（窒素吸着法） 100m2／ｇ
(4) ユナイテドMT（ユナイテドカーボン社製カ
ーボンブラツク〔MT〕）
DBP吸油量 35ml／100g
表面積（窒素吸着法） ６m2／ｇ
(5) Di−Cup40C（Hercules Powderco.U.S.A）
(6) ジブチルフタレート（DBP）
実施例 １〜７
次表にも示す通り、布々の各配合剤を種々の重
量部で配合して成る配合物をオープンロールで十
分混練した後、押出機にて内径40φで厚さ1.7mm
のホース状物を押出し、それをただちに温度250
℃に保たれた円筒状の常圧加硫管（この加硫管は
押出されたホースが入つてから出るまでに１分間
を要す長さのものであり、連続的に加硫すること
が可能な構造となつている。）に導入させ、加硫
されたホースを製造し、更にその加硫されたホー
スを切り開き、ダンベル状３号形の打ち抜き型で
打ち抜くことによりJIS−Ｋ−6301（加硫ゴムの
試験方法）の方法に適した試料を作成した。
次に、試料について、外観はその表面および切
断面を目視により発泡の有無を観察し、しかも引
張強さ、伸びおよび硬さはJIS−Ｋ−6301の方法
で試験を行ない、その結果を次表に示す。
比較例 １
次表にも示す通り、この場合はカーボンブラツ
ク(2)を2.0重量部とした以外は実施例１〜７の場
合と同様な方法にて試料を作成し、しかも実施例
１〜７の場合と同様な観察および試験を行ない、
その結果を次表に示す。
比較例 ２
次表にも示す通り、この場合はカーボンブラツ
ク(2)を40.0重量部とした以外は実施例１〜７と同
様な配合としたが、ロールによる充分な混練り作
業を行なつてもロール巻きにならず（配合物が一
体的に連ならない）、よつて試料を作成すること
ができないことから観察および試験ができず、結
局特性を見ることができなかつた。
この場合、ロール作業中ロール巻きができなか
つた原因はカーボン量の増量が影響したと思われ
る。
比較例 ３
次表に示す通り、この場合はカーボンブラツク
(2)の代りにカーボンブラツク(3)を50.0重量部を用
いた以外は実施例１〜７の場合と同様な方法にて
試料を作成し、しかも実施例１〜７の場合と同様
な観察および試験を行ない、その結果を次表に示
す。
比較例 ４
次表に示す通り、この場合は実施例５と同じ配
合から成る配合物を実施例５の場合と同様な押出
方法でホース状物を押出し、ただちにその押出さ
れたホースを冷却し、その後そのホースを切開
き、これを100×110mmで厚さ1.5mmの金型に入
れ、熱板を有するプレスにて100Kg／cm2に加圧
し、しかも160℃にて15分加熱し、加硫シートを
製造し、これを前述した場合と同様に打ち抜き型
によりJIS−Ｋ−6301の方法に用いることに適し
た試料を作成し、しかもその試料の試験等につい
ては実施例５と同様なことを行ない、その結果を
次表に示す。
[Industrial Application Field] The present invention relates to a urethane rubber composition that can be vulcanized at normal pressure. [Prior Art] Vulcanization of a rubber composition is a crosslinking reaction between rubber and a vulcanizing agent. In this crosslinking reaction, by-products are produced, and moisture, kneading air, etc. trapped in the rubber composition are evaporated by heating. Usually, in the rubber vulcanization process, press vulcanization or vulcanization can vulcanization is performed in order to prevent foaming defects due to volatilization of crosslinking reaction by-products, moisture, kneading air, etc. Now, in the vulcanization of rubber compositions, peroxide vulcanization is most likely to cause foaming defects because it involves a decomposition reaction of peroxide. In particular, in peroxide-cured ester-based urethane rubber compositions, a large amount of by-products are produced due to the crosslinking reaction between the peroxide and the ester-based urethane rubber, so poor foaming is unavoidable during normal pressure vulcanization. For this reason, it has been difficult to make long or large atmospheric pressure vulcanized molded products from ester-based urethane rubber compositions. [Problems to be Solved by the Invention] The present invention has been made based on the above-mentioned points, and solves the above-mentioned drawbacks of the prior art and provides a normal method that does not cause foaming defects even when vulcanized at normal pressure. An object of the present invention is to provide a urethane rubber composition that can be pressure vulcanized. [Means for Solving the Problems] The gist of the present invention is to provide a urethane rubber composition containing peroxide and conductive carbon black, in which the urethane rubber is an ester-based urethane rubber; Based on ASTM-D2414 for 100 parts by weight of ester-based urethane rubber.
A urethane rubber that can be vulcanized at atmospheric pressure and is characterized by containing 3 to 18 parts by weight of conductive carbon black with a DBP oil absorption of 250 ml/100 g or more and a surface area of 500 m 2 /g or more by nitrogen adsorption method. In the composition. In the present invention, the ester-based urethane rubber is a urethane rubber obtained from a polyester oligomer and a polyisocyanate, and is commercially available industrially as Urepane 640 from Bayer AG, West Germany. The reason why the urethane rubber in the present invention is limited to ester-based urethane rubber is that although it can improve abrasion resistance and chemical resistance compared to ether-based urethane rubber, foaming failures are likely to occur frequently due to crosslinking reaction by-products. In the present invention, the oil absorption amount of ordinary carbon blacks such as furnace blacks, thermal blacks, channel blacks, or acetylene blacks is 250%.
ml/100g or less and surface area measured by nitrogen deposition method is 500
Foaming cannot be suppressed because it is small, less than m 2 /g. On the other hand, the conductive carbon black used in the present invention has an oil absorption capacity of 250 ml/ml, which has an anti-foaming effect.
It is a special material with a weight of 100 g or more and a surface area of 500 m 2 /g or more, and has never been blended into urethane rubber or the like. In the present invention, the content of this special conductive carbon black is limited to 3 to 18 parts by weight.
This is because if it is less than 18 parts by weight, it will not have a foaming inhibiting effect, and if it is more than 18 parts by weight, it will not be able to exhibit a foaming inhibiting effect proportional to the amount blended, and since it is a special carbon black, it will lead to a rapid increase in price. [Function] The function of the present invention is that the ester-based urethane rubber 100
By blending 3 to 18 parts by weight of conductive carbon black with a DBP oil absorption of 250 ml/100 g or more according to ASTM-D2414 and a surface area of 500 m 2 /g or more according to the nitrogen adsorption method, ester-based urethane Its purpose is to adsorb a large amount of volatile components produced by the crosslinking reaction between rubber and peroxide, thereby effectively suppressing foaming even when vulcanized at normal pressure. [Examples] Hereinafter, the urethane rubber composition of the present invention will be explained in more detail with reference to some examples. The formulation materials (numbers in parentheses in the formulation column) used in these Examples and Comparative Examples are as follows. (1) Urepane 640 (manufactured by West German Bayer AG) (2) Ketsuchen Black EC (Nippon EC Co., Ltd.)
DBP oil absorption 350ml/100g Surface area (nitrogen adsorption method) 950m 2 /g (3) Seast 3 (Tokai Electrode Carbon Black [HAF]) DBP oil absorption 102ml/100g Surface area (nitrogen adsorption method) 100m 2 /g ( 4) United MT (United Carbon Co., Ltd. carbon black [MT]) DBP oil absorption 35ml/100g Surface area (nitrogen adsorption method) 6m 2 /g (5) Di-Cup40C (Hercules Powderco.USA) (6) Dibutyl phthalate ( DBP) Examples 1 to 7 As shown in the following table, after thoroughly kneading the compositions made of various parts by weight of each compounding agent of the cloth using an open roll, an extruder was used to mix the compositions with an inner diameter of 40φ and a thickness of 40 mm. 1.7mm
extrude the hose and immediately bring it to a temperature of 250
A cylindrical atmospheric pressure vulcanization tube kept at ℃ (this vulcanization tube is long enough for the extruded hose to enter and exit for one minute, and cannot be continuously vulcanized. JIS-K-6301 ( A sample suitable for the test method for vulcanized rubber was prepared. Next, the appearance of the sample was visually observed on the surface and cut surface for the presence or absence of foaming, and the tensile strength, elongation, and hardness were tested using the JIS-K-6301 method, and the results are shown in the table below. Shown below. Comparative Example 1 As shown in the following table, samples were prepared in the same manner as in Examples 1 to 7 except that carbon black (2) was used in this case at 2.0 parts by weight. Perform the same observations and tests as in the case of
The results are shown in the table below. Comparative Example 2 As shown in the following table, in this case, the same formulation as in Examples 1 to 7 was used except that carbon black (2) was used at 40.0 parts by weight, but sufficient kneading with rolls was carried out. However, it was not possible to form a roll (the mixture was not continuous), and as a result, it was impossible to prepare a sample, so observation and testing were not possible, and in the end, the characteristics could not be observed. In this case, it is thought that the increase in the amount of carbon was the reason why the roll could not be completed during the roll operation. Comparative Example 3 As shown in the table below, in this case carbon black
Samples were prepared in the same manner as in Examples 1 to 7, except that 50.0 parts by weight of carbon black (3) was used instead of (2), and observations were made in the same manner as in Examples 1 to 7. The results are shown in the table below. Comparative Example 4 As shown in the following table, in this case, a hose-shaped article was extruded using the same extrusion method as in Example 5 using the same formulation as in Example 5, and the extruded hose was immediately cooled. After that, cut out the hose, put it into a mold with a size of 100 x 110 mm and a thickness of 1.5 mm, pressurize it to 100 kg/cm 2 with a press equipped with a hot plate, and heat it at 160°C for 15 minutes to vulcanize it. A sheet was manufactured, and a sample suitable for use in the method of JIS-K-6301 was prepared using a punching die in the same manner as described above, and the test of the sample was conducted in the same manner as in Example 5. The results are shown in the table below.
本発明の常圧加硫可能なウレタンゴム組成物
は、プレス加硫や罐加硫のような大型の加圧加硫
装置を必要とせず、常圧において加熱加硫できる
るエステル系ウレタンゴム組成物であり、長尺あ
るいは大型のウレタンゴム成形品用ウレタンゴム
組成物として工業上有用である。
The urethane rubber composition that can be vulcanized at normal pressure according to the present invention is an ester-based urethane rubber composition that can be heat-vulcanized at normal pressure without requiring a large-scale pressure vulcanization device such as press vulcanization or can vulcanization. It is industrially useful as a urethane rubber composition for long or large urethane rubber molded products.
Claims (1)
して成るウレタンゴム組成物において、ウレタン
ゴムがエステル系ウレタンゴムであつて、該エス
テル系ウレタンゴム100重量部に対し、ASTM−
D2414によりDBP吸油量が250ml／100g以上でか
つ窒素吸着法による表面積が500m2／ｇ以上であ
る導電性カーボンブラツク３〜18重量部配合して
成ることを特徴とする常圧加硫可能なウレタンゴ
ム組成物。1. In a urethane rubber composition formed by blending peroxide and conductive carbon black, the urethane rubber is an ester-based urethane rubber, and the ASTM-
A urethane that can be vulcanized at atmospheric pressure and is characterized by containing 3 to 18 parts by weight of conductive carbon black, which has a DBP oil absorption of 250 ml/100 g or more according to D2414 and a surface area of 500 m 2 /g or more by nitrogen adsorption method. Rubber composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56168305A JPS5869247A (en) | 1981-10-21 | 1981-10-21 | Urethane rubber composition that can be vulcanized at normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56168305A JPS5869247A (en) | 1981-10-21 | 1981-10-21 | Urethane rubber composition that can be vulcanized at normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5869247A JPS5869247A (en) | 1983-04-25 |
| JPS6116294B2 true JPS6116294B2 (en) | 1986-04-30 |
Family
ID=15865552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56168305A Granted JPS5869247A (en) | 1981-10-21 | 1981-10-21 | Urethane rubber composition that can be vulcanized at normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5869247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6423387U (en) * | 1987-07-29 | 1989-02-07 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791453B2 (en) * | 1986-10-08 | 1995-10-04 | 株式会社スリ−ボンド | Conductive resin composition |
-
1981
- 1981-10-21 JP JP56168305A patent/JPS5869247A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6423387U (en) * | 1987-07-29 | 1989-02-07 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5869247A (en) | 1983-04-25 |
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