JPS62277445A - Light color rubber composition - Google Patents
Light color rubber compositionInfo
- Publication number
- JPS62277445A JPS62277445A JP12199886A JP12199886A JPS62277445A JP S62277445 A JPS62277445 A JP S62277445A JP 12199886 A JP12199886 A JP 12199886A JP 12199886 A JP12199886 A JP 12199886A JP S62277445 A JPS62277445 A JP S62277445A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- halogen
- composition
- butadiene copolymer
- light
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 78
- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- -1 polyethylene Polymers 0.000 claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 5
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 5
- 229920001194 natural rubber Polymers 0.000 claims abstract description 5
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 5
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 4
- 150000001993 dienes Chemical class 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 17
- 239000000049 pigment Substances 0.000 abstract description 10
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 7
- 239000005061 synthetic rubber Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 description 8
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- 101100314299 Listeria innocua serovar 6a (strain ATCC BAA-680 / CLIP 11262) tpi-2 gene Proteins 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 ３、発明の詳細な説明 瓜呈上立机旦光ユ 本発明は、明色ゴム組成物に関する。[Detailed description of the invention] 3. Detailed description of the invention Gourmet standing machine Danguangyu The present invention relates to light colored rubber compositions.
ｌ米二及土
分子中にハロゲン原子を含む合成ゴム、特に、ポリクロ
ロプレンゴムやポリクロロスルホン化ポリエチレンゴム
は、加硫に際して脱塩酸が生じて、ゴムが黒色を帯びる
ので、例えば、酸化チタンや有色有機顔料のような隠蔽
力の強い顔料を多量に配合して、加硫時の黒色化を１！
！蔽するように、所謂明色配合がなされている。Synthetic rubbers containing halogen atoms in their molecules, especially polychloroprene rubber and polychlorosulfonated polyethylene rubber, undergo dehydrochloric acid removal during vulcanization and turn the rubber blackish. By blending a large amount of pigments with strong hiding power such as colored organic pigments, the blackening during vulcanization is 1!
! A so-called bright color combination is used to cover the area.
■が解゛°シようとする０Ｉ題点
しかし、このように顔料を多量に配合するハロゲン含有
ゴム明色配合は、他方において、その加硫ゴムの引張強
さ、伸び、モジュラス等を低下させるほか、加硫ゴム製
品が接触する部材に顔料の転色を生じ、また、加硫ゴム
製品の価格を高めることとなる。他方、加硫の際の若干
の黒色化を是認して、Ｉｘｒｉ料の配合量を少量にとど
めても、加硫の温度や時間による熱履歴によって、黒色
化の度合が著しく異なり、色のばらつきが大きいので、
商品価値に劣り、実用に供し難い。0I problem that ① tries to solve However, on the other hand, light-colored formulations of halogen-containing rubbers that incorporate large amounts of pigments also reduce the tensile strength, elongation, modulus, etc. of the vulcanized rubber. In addition, discoloration of pigments occurs on members with which the vulcanized rubber product comes into contact, and the price of the vulcanized rubber product increases. On the other hand, even if some blackening is allowed during vulcanization and the amount of Ixri compound is kept to a small amount, the degree of blackening will vary significantly depending on the heat history due to the temperature and time of vulcanization, resulting in color variation. is large, so
It has inferior commercial value and is difficult to put into practical use.
本発明者らは、従来のポリクロロプレンゴムやポリクロ
ロスルホン化ポリエチレンゴムの明色配合における上記
した問題を解決するために鋭意研究した結果、ハロゲン
原子を含む合成ゴムにハロゲン原子を含まないジオレフ
ィン系ゴムを配合することによって、顔料の配合量を少
量に抑えつつ、上記ハロゲン含有ゴムの加硫時の黒色化
を有効に防止することができることを見出して、本発明
に至ったものである。The present inventors have conducted intensive research to solve the above-mentioned problems in light-colored formulations of conventional polychloroprene rubber and polychlorosulfonated polyethylene rubber. The present invention was achieved based on the discovery that blackening of the halogen-containing rubber during vulcanization can be effectively prevented by blending the halogen-containing rubber while keeping the amount of pigment blended to a small amount.
同■んｚ４すＵンり旨ケへ１役
本発明による明色ゴム組成物は、ポリクロロプレンゴム
及びポリクロロスルホン化ポリエチレンゴムより選ばれ
るハロゲン含有ゴム重合体を含む明色配合組成物におい
て、上記ハロゲン含有ゴム重合体の３〜４０重世％が分
子内にハロゲンを含有しないジオレフィン系ゴム重合体
にて置換されていることを特徴とする。The light colored rubber composition according to the present invention is a light colored compound composition containing a halogen-containing rubber polymer selected from polychloroprene rubber and polychlorosulfonated polyethylene rubber. It is characterized in that 3 to 40 times % of the halogen-containing rubber polymer is substituted with a diolefin rubber polymer that does not contain a halogen in the molecule.
本発明において用いるジオレフィン系ゴムは、分子内に
二重結合を有するゴムであれば、限定されるものではな
いが、本発明において特に好ましいジオレフィン系ゴム
として、ポリブタジェンゴム、ポリイソプレンゴム、ス
チレン−ブタジエン共重合体ゴム、アクリロニトリル−
ブタジエン共重合体ゴム及び天然ゴムを挙げることがで
きる。The diolefin rubber used in the present invention is not limited as long as it has a double bond in the molecule, but particularly preferred diolefin rubbers in the present invention include polybutadiene rubber and polyisoprene rubber. , styrene-butadiene copolymer rubber, acrylonitrile-
Mention may be made of butadiene copolymer rubber and natural rubber.
これらは単独にて、又は２以上の混合物として配合され
る。These may be used alone or as a mixture of two or more.
本発明によれば、ポリクロロプレンゴム及びポリクロロ
スルホン化ポリエチレンゴムより選ばれるハロゲン含有
ゴム重合体の３〜４０重量％を上記ジオレフィン系ゴム
にて置換することによって、その加硫時の黒色化を効果
的に防止することができる。上記ハロゲン含有ゴムにお
けるジオレフィン系ゴムの置換量が３重量％よりも少な
いときは、加硫時の黒色化を尚避けることがでない。他
方、４０重量部を越えるときは、加硫に際しての変色は
ないが、ジオレフィン系ゴムが連続相を形成し、ハロゲ
ン含有ゴムの特性を失わせるので、本来、かかるゴム重
合体を用いる理由がなくなり、また、種々のゴム物性が
劣化する。According to the present invention, by replacing 3 to 40% by weight of the halogen-containing rubber polymer selected from polychloroprene rubber and polychlorosulfonated polyethylene rubber with the diolefin rubber, blackening is achieved during vulcanization. can be effectively prevented. When the amount of diolefin rubber substituted in the halogen-containing rubber is less than 3% by weight, blackening during vulcanization cannot be avoided. On the other hand, if the amount exceeds 40 parts by weight, there will be no discoloration during vulcanization, but the diolefin rubber will form a continuous phase and the properties of the halogen-containing rubber will be lost. In addition, various rubber properties deteriorate.
本発明において、上記ハロゲン含有ゴム重合体の加硫は
、イオウ加硫でも、金属酸化物加硫でもよく、いずれの
場合にも、加硫時の黒色化を有効に防止することができ
る。In the present invention, the halogen-containing rubber polymer may be vulcanized by sulfur vulcanization or metal oxide vulcanization, and in either case, blackening during vulcanization can be effectively prevented.
更に、本発明においては、ハロゲン含有ゴム重合体に、
通常、配合される配合剤、例えば、補強剤、充填剤、オ
イル、老化防止剤、加硫剤、加硫促進剤等のゴム配合剤
を適宜量配合してよいのは勿論である。Furthermore, in the present invention, the halogen-containing rubber polymer contains
Of course, appropriate amounts of rubber compounding agents such as reinforcing agents, fillers, oils, anti-aging agents, vulcanizing agents, and vulcanization accelerators, which are usually compounded, may be compounded.
本発明による明色ゴム配合によって、加硫時の黒色化が
防止される理由は必ずしも明らかではないが、脱塩酸に
よって生成した塩化水素がジオレフィン系ゴムが分子内
に有する二重結合に付加するためであるとみられる。し
かし、本発明は、黒色化の防止の機構によって何ら制限
されるものではない。The reason why the light-colored rubber composition according to the present invention prevents blackening during vulcanization is not necessarily clear, but the reason is that hydrogen chloride generated by dehydrochlorination is added to the double bonds that the diolefin rubber has in its molecules. This appears to be for the purpose of this. However, the present invention is not limited in any way by the mechanism for preventing blackening.
発］坏ｌ伽里
以上のように、本発明によれば、ポリクロロプレンゴム
及びポリクロロスルホン化ポリエチレンゴムより選ばれ
るハロゲン含有ゴム重合体の３〜４０重量％をジオレフ
ィン系ゴｌ、にて置換することによって、少量の顔料を
配合するのみで、安定して、加硫時の黒色化を防止する
ことができ、しかも、得られる加硫ゴム製品は、顔料の
配合量が少ないために、ハロゲン含有ゴムのすぐれた物
性をよく保持している。更に、顔料を多量に用いないの
で、加硫ゴム製品を低度に製造することができ、また、
かかる加硫ゴム製品は、接触する物品に対しても、顔料
の転色が起こらない。As described above, according to the present invention, 3 to 40% by weight of the halogen-containing rubber polymer selected from polychloroprene rubber and polychlorosulfonated polyethylene rubber is mixed with diolefin rubber. By substitution, it is possible to stably prevent blackening during vulcanization by adding only a small amount of pigment, and the resulting vulcanized rubber product has a small amount of pigment. It retains the excellent physical properties of halogen-containing rubber. Furthermore, since large amounts of pigments are not used, vulcanized rubber products can be manufactured at low levels, and
Such vulcanized rubber products do not cause discoloration of pigments even on articles that come into contact with them.
去施±
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
第１表に示すイオウ加硫系ポリクロロプレンゴム明色配
合にアクリロニトリル−ブタジエン共重合体ゴムを種々
の量にて配合し、１５０°Ｃで３０分間加熱する加硫条
件にてＡＳＴＭ ２ ＊ｎスラブに加硫した。変色度合
を第１表に示す。尚、変色度合は、ポリクロロプレンゴ
ム１００％配合の場合を１０、ＮＢＲ１００％配合の場
合を１とする１０段階評価によった（以下も同じ）。Example 1 Various amounts of acrylonitrile-butadiene copolymer rubber were blended into the light-colored sulfur-vulcanized polychloroprene rubber composition shown in Table 1, and ASTM 2 was obtained under vulcanization conditions of heating at 150°C for 30 minutes. *Vulcanized into n slab. Table 1 shows the degree of discoloration. The degree of discoloration was evaluated on a 10-point scale with 10 being 100% polychloroprene rubber and 1 being 1 being 100% NBR (the same applies below).
実施例２
第２表に示すイオウ加硫系ポリクロロプレンゴム明色配
合にアクリロニトリル−ブタジエン共重合体ゴム（日本
合成ゴム■製Ｎ２５Ｏ３） 、スチレン−ブタジエンゴ
ム（日本合成ゴム側製ＳＢＲ１５０２）、ブタジェンゴ
ム（日本合成ゴム■製ＪＳＲＢＲ０１）、イソプレンゴ
ム（日本合成ゴム■製Ｊ’ＳＲＩＲ２２００）又は天然
ゴムを１０重量部配合し、実施例１と同じ条件にてＡＳ
ＴＰｉ ２ ｔｍスラブを得た。変色度合を第２表に示
す。Example 2 Acrylonitrile-butadiene copolymer rubber (N25O3 manufactured by Nippon Synthetic Rubber), styrene-butadiene rubber (SBR1502 manufactured by Nippon Synthetic Rubber), and butadiene rubber (SBR1502 manufactured by Nippon Synthetic Rubber) were added to the light-colored sulfur-vulcanized polychloroprene rubber composition shown in Table 2 10 parts by weight of isoprene rubber (JSRBR01 manufactured by Nippon Synthetic Rubber ■), isoprene rubber (J'SRIR2200 manufactured by Nippon Synthetic Rubber ■), or natural rubber were mixed and AS was prepared under the same conditions as in Example 1.
A TPi 2 tm slab was obtained. Table 2 shows the degree of discoloration.
第２表
このように、同じ配合量にてその効果が異なるのは、加
硫時に発生する塩化水素を捕捉するジオレフィン系ゴム
重合体の二重結合量に依存するためであるとみられる。Table 2 The reason why the effects differ even with the same blending amount is considered to be because it depends on the amount of double bonds in the diolefin rubber polymer that captures hydrogen chloride generated during vulcanization.
例えば、アクリロニトリル−ブタジエン共重合体ゴムや
スチレン−ブタジエン共重合体ゴムに比較して、ポリブ
タジェンゴム、ポリイソプレンゴム及び天然ゴムは、配
合量が同じであるとき、その二重結合量が多いために、
黒色化の効果にすぐれるのであろう。For example, compared to acrylonitrile-butadiene copolymer rubber and styrene-butadiene copolymer rubber, polybutadiene rubber, polyisoprene rubber, and natural rubber have a higher double bond content when the amount is the same. for,
It probably has an excellent blackening effect.
実施例３
第３表に示す金属酸化物加硫系ポリクロロプレンゴム明
色配合にアクリロニトリル−ブタジエン共重合体ゴム１
０重量部配合し、実施例１と同じ条件にてＡＳＴＭ ２
龍スラブに加硫した。変色度合を第３表に示す。Example 3 Acrylonitrile-butadiene copolymer rubber 1 was added to the metal oxide vulcanized polychloroprene rubber light-colored formulation shown in Table 3.
0 parts by weight and ASTM 2 under the same conditions as Example 1.
Vulcanized into a dragon slab. Table 3 shows the degree of discoloration.
第３表
実施例４
第４表に示すポリクロロスルホン化ポリエチレンゴム明
色配合にアクリロニトリル−ブタジエン共重合体ゴム１
０重量部配合し、実施例１と同じ条件にてＡＳＴＭ ２
龍スラブに加硫した。変色度合を第４表に示す。Table 3 Example 4 Acrylonitrile-butadiene copolymer rubber 1 is added to the light color combination of polychlorosulfonated polyethylene rubber shown in Table 4.
0 parts by weight and ASTM 2 under the same conditions as Example 1.
Vulcanized into a dragon slab. Table 4 shows the degree of discoloration.
第４表
（注）■）ポリクロロスルホン化ポリエチレンゴム（昭
和ネオプレン■製ハイパロン４０）２）ジペンタメチレ
ンチウラムテトラスルフイドTable 4 (Note) ■) Polychlorosulfonated polyethylene rubber (Hypalon 40 manufactured by Showa Neoprene ■) 2) Dipentamethylene thiuram tetrasulfide
Claims (2)
ポリエチレンゴムより選ばれるハロゲン含有ゴム重合体
を含む明色配合組成物において、上記ハロゲン含有ゴム
重合体の３〜４０重量％が分子内にハロゲンを含有しな
いジオレフィン系ゴム重合体にて置換されていることを
特徴とする明色ゴム組成物。(1) In a light-colored compounded composition containing a halogen-containing rubber polymer selected from polychloroprene rubber and polychlorosulfonated polyethylene rubber, 3 to 40% by weight of the halogen-containing rubber polymer does not contain halogen in the molecule. A light-colored rubber composition characterized in that it is substituted with a diolefin rubber polymer.
プレンゴム、ポリブタジエンゴム、アクリロニトリル−
ブタジエン共重合体ゴム及びスチレン−ブタジエン共重
合体ゴムよりなる群から選ばれる少なくとも１種である
ことを特徴とする特許請求の範囲第１項記載の明色ゴム
組成物。(2) The diolefin rubber polymer is natural rubber, polyisoprene rubber, polybutadiene rubber, or acrylonitrile.
The light-colored rubber composition according to claim 1, characterized in that the light-colored rubber composition is at least one member selected from the group consisting of butadiene copolymer rubber and styrene-butadiene copolymer rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61121998A JPH0689180B2 (en) | 1986-05-27 | 1986-05-27 | Light color rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61121998A JPH0689180B2 (en) | 1986-05-27 | 1986-05-27 | Light color rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62277445A true JPS62277445A (en) | 1987-12-02 |
| JPH0689180B2 JPH0689180B2 (en) | 1994-11-09 |
Family
ID=14825027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61121998A Expired - Lifetime JPH0689180B2 (en) | 1986-05-27 | 1986-05-27 | Light color rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689180B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018131565A (en) * | 2017-02-16 | 2018-08-23 | 東ソー株式会社 | Rubber composition, compound, vulcanizate and rubber roll |
| JP2019099799A (en) * | 2017-12-05 | 2019-06-24 | 東ソー株式会社 | Rubber composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113848A (en) * | 1974-07-26 | 1976-02-03 | Nippon Zeon Co | JENKEI JUGOTAIGO MUSOSEIBUTSU |
| JPS51114451A (en) * | 1975-04-02 | 1976-10-08 | Nippon Zeon Co Ltd | Diene rubber composition |
| JPS5630445A (en) * | 1979-08-17 | 1981-03-27 | Degussa | Vulcanizable rubber mixture* its vulcanization and manufacture of tire* its tread* industrial rubber product and shoe sole |
| JPS5657839A (en) * | 1979-10-16 | 1981-05-20 | Seikou Kagaku Kk | Chloroprene rubber composition |
-
1986
- 1986-05-27 JP JP61121998A patent/JPH0689180B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113848A (en) * | 1974-07-26 | 1976-02-03 | Nippon Zeon Co | JENKEI JUGOTAIGO MUSOSEIBUTSU |
| JPS51114451A (en) * | 1975-04-02 | 1976-10-08 | Nippon Zeon Co Ltd | Diene rubber composition |
| JPS5630445A (en) * | 1979-08-17 | 1981-03-27 | Degussa | Vulcanizable rubber mixture* its vulcanization and manufacture of tire* its tread* industrial rubber product and shoe sole |
| JPS5657839A (en) * | 1979-10-16 | 1981-05-20 | Seikou Kagaku Kk | Chloroprene rubber composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018131565A (en) * | 2017-02-16 | 2018-08-23 | 東ソー株式会社 | Rubber composition, compound, vulcanizate and rubber roll |
| JP2019099799A (en) * | 2017-12-05 | 2019-06-24 | 東ソー株式会社 | Rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689180B2 (en) | 1994-11-09 |
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