JPH03157434A - Additive for modifying rubber - Google Patents
Additive for modifying rubberInfo
- Publication number
- JPH03157434A JPH03157434A JP29528589A JP29528589A JPH03157434A JP H03157434 A JPH03157434 A JP H03157434A JP 29528589 A JP29528589 A JP 29528589A JP 29528589 A JP29528589 A JP 29528589A JP H03157434 A JPH03157434 A JP H03157434A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- salt
- additive
- formula
- 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.)
- Pending
Links
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title abstract description 47
- 239000005060 rubber Substances 0.000 title abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 16
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 abstract description 4
- 229940007718 zinc hydroxide Drugs 0.000 abstract description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 abstract description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000920 calcium hydroxide Substances 0.000 abstract description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011575 calcium Chemical class 0.000 abstract 2
- 239000011777 magnesium Chemical class 0.000 abstract 2
- 239000011701 zinc Substances 0.000 abstract 2
- 238000004073 vulcanization Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XPTAYXCXYFWRIF-UHFFFAOYSA-N (2-hydroxy-2-oxo-1,3,2lambda5-dioxaphospholan-4-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1COP(O)(=O)O1 XPTAYXCXYFWRIF-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000010060 peroxide vulcanization Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 238000010059 sulfur vulcanization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- -1 8M) Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ゴム中に配合してゴムを改質するために用い
るゴム改質用添加剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a rubber-modifying additive that is blended into rubber and used to modify the rubber.
〔従来の技術及び発明が解決しようとする課題〕従来、
ゴムを改質して目的とする用途に適合させるため、ゴム
原料中に改質用添加剤を配合する（但し、Ｒは水素原子
又はメチル基、ｎは１又は２である。）
で示される化合物がある。この（１）式の化合物は、分
子内にアクリル基と２価リン酸基を有する化合物であり
、その構造から考えてゴム用の共架橋剤として、或いは
イオン架橋剤として作用する可能性があるが、これまで
ゴム用添加剤として使用された例はなく、そのゴムへの
配合効果についても明らかにされていない。これは、（
１）・式の化合物が粘稠な液状であるためロール加工性
が悪く、ゴム配合剤の亜鉛華等と反応して分散不良を起
こし易いことが原因の一つであると考えられる。このた
め、（１）式の化合物はゴム用に全く利用されていない
のが実情であった。[Problems to be solved by conventional techniques and inventions] Conventionally,
In order to modify the rubber and make it suitable for the intended use, a modifying additive is blended into the rubber raw material (where R is a hydrogen atom or a methyl group, and n is 1 or 2). There are compounds. This compound of formula (1) has an acrylic group and a divalent phosphate group in its molecule, and considering its structure, it may act as a co-crosslinking agent for rubber or as an ionic crosslinking agent. However, there have been no examples of its use as an additive for rubber, and the effects of its addition to rubber have not been clarified. this is,(
One of the reasons is thought to be that the compound of formula 1) has poor roll processability because it is a viscous liquid, and tends to react with zinc white, etc. of the rubber compounding agent, resulting in poor dispersion. For this reason, the actual situation is that the compound of formula (1) has not been used at all for rubber.
本発明は、上記事情に鑑みなされたもので、上記（１）
式の化合物を利用した優れたゴム改質効果を有する新規
ゴム用添加剤を提供することを目的とする。The present invention was made in view of the above circumstances, and includes the above (1).
The object of the present invention is to provide a new rubber additive having an excellent rubber-modifying effect using a compound of the formula.
〔課題を解決するための手段及び作用〕本発明者らは、
上記目的を達成するため、（１）式の化合物の１つであ
る下記式（１ａ）で示されるモノメタクリロイルオキシ
エチレンホスフェート（ＰＭ−１）のゴムへの配合につ
いて種々研究を行なっているーうち、ＰＭ−１の亜鉛塩
、マグネシウム塩、アルミニウム塩又はカルシウム塩を
ゴムに配合した場合、この塩が亜鉛華等と反応すること
もなくゴム中に均一に分散されることを見い出した。そ
して、本発明者らは、更に上記ＰＭ−１の塩のゴムへの
配合効果について検討を行なった結果、これらＰＭ−１
の塩が特有のゴム改質効果を示し、ゴム改質剤として有
効に使用し得ることを知見し、本発明をなすに至った。[Means and effects for solving the problem] The present inventors,
In order to achieve the above objective, we are conducting various studies on the incorporation of monomethacryloyloxyethylene phosphate (PM-1) shown by the following formula (1a), which is one of the compounds of formula (1), into rubber. It has been found that when a zinc salt, magnesium salt, aluminum salt, or calcium salt of PM-1 is blended into rubber, this salt does not react with zinc white or the like and is uniformly dispersed in the rubber. The present inventors further investigated the effect of blending the PM-1 salt into rubber, and found that these PM-1 salts
The present inventors have discovered that the salts of these compounds exhibit a unique rubber-modifying effect and can be effectively used as rubber modifiers, leading to the present invention.
従って、本発明は、下記式（１）
（但し、Ｒは水素原子又はメチル基、ｎは１又は２であ
る。）
で示される化合物の亜鉛塩、マグネシウム塩、アルミニ
ウム塩又はカルシウム塩からなることを特徴とするゴム
改質用添加剤を提供する。Therefore, the present invention consists of a zinc salt, magnesium salt, aluminum salt, or calcium salt of a compound represented by the following formula (1) (wherein R is a hydrogen atom or a methyl group, and n is 1 or 2). Provided is an additive for rubber modification characterized by the following.
この場合、（１）式の化合物としては、Ｒがメチル基で
ｎ＝１のものが特に好ましい。In this case, the compound of formula (1) is particularly preferably one in which R is a methyl group and n=1.
また、本発明の添加剤は、粉末状、特に粒径１０〜０．
１Ｍ程度の粉末状に形成することが好ましく、これによ
りゴム中における分散性が向上する。Further, the additive of the present invention may be in powder form, particularly with a particle size of 10 to 0.
It is preferable to form it into a powder of about 1M, which improves the dispersibility in the rubber.
更に、本発明の添加剤は、（１）式の化合物の上記４種
の塩のうち２種以上を混合することにより調製すること
もできる。Furthermore, the additive of the present invention can also be prepared by mixing two or more of the above four types of salts of the compound of formula (1).
なお１本発明添加剤の製法に限定はないが、例えば（１
）式の化合物と水酸化亜鉛、水酸化マグネシウム、水酸
化アルミニウム、水酸化カルシウム等とを適宜手段で反
応させることにより製造することができる。Note that there is no limitation on the manufacturing method of the additive of the present invention, but for example (1
) can be produced by reacting a compound of the formula with zinc hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, etc. by an appropriate means.
本発明の添加剤は、ゴムを改質する目的でゴム中に配合
されるものであるが、この場合ゴムの種類に制限はなく
、本発明添加剤は例えばブタジェンゴム（ＢＲ）、スチ
レン−ブタジェンゴム（ＳＢＲ）、アクリロニトリル−
ブタジェンゴム（ＮＢＲ）、イソプレンゴム（天然ゴム
）、クロロプレンゴム（ＣＲ）等のジエン系ゴム、エチ
レンプロピレンゴム（ＥＰＤＭ）、塩素化ポリエチレン
ゴム（ＣＭ）、クロルスルホン化ポリエチレンゴム（Ｃ
８Ｍ）等のオレフィン系ゴム、ポリエステル−イソシア
ナート、ポリエーテルイソシアナート等のウレタン系ゴ
ム、アクリル酸エステルポリマー等のビニル系ゴムなど
の種々のゴムの改質に好適に使用される。The additive of the present invention is blended into rubber for the purpose of modifying the rubber, but in this case there is no restriction on the type of rubber, and the additive of the present invention is, for example, butadiene rubber (BR), styrene-butadiene rubber ( SBR), acrylonitrile-
Diene rubbers such as butadiene rubber (NBR), isoprene rubber (natural rubber), chloroprene rubber (CR), ethylene propylene rubber (EPDM), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (C
It is suitably used for modifying various rubbers such as olefin rubbers such as 8M), urethane rubbers such as polyester-isocyanate and polyether isocyanate, and vinyl rubbers such as acrylic acid ester polymers.
また１本発明の添加剤はパーオキサイド加硫、硫黄加硫
等のいずれの加硫方式のゴムに対しても有効に使用でき
る。例えば後述する実施例に示すようにパーオキサイド
加硫系ゴムの改質に（１）式の化合物の亜鉛塩、マグネ
シウム塩を用いた場合にはモジュラス、引張強さ、硬度
が改善される。Furthermore, the additive of the present invention can be effectively used for rubbers cured by any of the vulcanization methods, such as peroxide vulcanization and sulfur vulcanization. For example, as shown in Examples below, when a zinc salt or magnesium salt of the compound of formula (1) is used to modify peroxide vulcanized rubber, the modulus, tensile strength, and hardness are improved.
また、硫黄加硫系ゴムの改質に（１）式の化合物の亜鉛
塩、マグネシウム塩を用いた場合には引張強さ及び伸び
が改善される。Furthermore, when a zinc salt or magnesium salt of the compound of formula (1) is used to modify sulfur-vulcanized rubber, the tensile strength and elongation are improved.
本発明添加剤のゴムへの配合量に特に限定はないが、ジ
エン系ゴム、オレフィン系ゴム等の原料ゴム１００重量
部に対して５〜５０重量部、特に５〜２０重量部とする
ことが好ましく、これにより本発明添加剤の改質効果が
良好に発揮される。There is no particular limitation on the amount of the additive of the present invention added to rubber, but it may be 5 to 50 parts by weight, particularly 5 to 20 parts by weight, per 100 parts by weight of raw rubber such as diene rubber, olefin rubber, etc. Preferably, this allows the modification effect of the additive of the present invention to be exhibited well.
また、ゴム中には公知の他の配合剤を適宜配合すること
ができ、例えばカーボンブラック、ホワイトカーボン、
ケイ酸マグネシウム、クレー、タルク、炭酸カルシウム
等の充填剤を原料ゴム１００重量部に対して１０〜２０
０重量部、ジクミルパーオキサイド、硫黄といったパー
オキサイド系や硫黄系等の加硫剤を原料ゴム１００重量
部に対して０．５〜５重量部、チオウレア類、チウラム
類。In addition, other known compounding agents can be appropriately blended into the rubber, such as carbon black, white carbon,
Add fillers such as magnesium silicate, clay, talc, and calcium carbonate to 10 to 20 parts by weight of raw rubber.
0 parts by weight, 0.5 to 5 parts by weight of peroxide-based or sulfur-based vulcanizing agents such as dicumyl peroxide and sulfur based on 100 parts by weight of raw rubber, thioureas, and thiurams.
ジチオカルバミン酸塩類等の加硫促進剤を原料ゴム１０
０重量部に対して０．１〜５重量部置部することができ
る。更に、ジオクチルフタレート（ＤＯＰ） 、パラフ
ィン系オイル、ナフテン系オイル、芳香族系オイル等の
軟化剤やフェノール系、アミン系の老化防止剤なども適
宜配合することができる。なお、本発明添加剤を配合し
たゴム配合物の加硫温度は１４０〜２００℃、加硫時間
は５〜６０分とすることが好適である。Vulcanization accelerators such as dithiocarbamates are added to raw rubber 10
The amount can be 0.1 to 5 parts by weight relative to 0 parts by weight. Furthermore, softeners such as dioctyl phthalate (DOP), paraffinic oils, naphthenic oils, and aromatic oils, and phenol-based and amine-based anti-aging agents can also be blended as appropriate. In addition, it is suitable that the vulcanization temperature of the rubber compound containing the additive of the present invention is 140 to 200°C, and the vulcanization time is 5 to 60 minutes.
以上説明したように、本発明のゴム用添加剤は特有のゴ
ム改質効果を有し、ジエン系ゴム、オレフィン系ゴム等
の種々のゴムの改質に有効に使用されるもので、ゴムの
用途の拡大に大きく寄与するものである。As explained above, the rubber additive of the present invention has a unique rubber modification effect and is effectively used for modifying various rubbers such as diene rubber and olefin rubber. This will greatly contribute to the expansion of applications.
次に、製造例、実施例、比較例を示し、本発明を具体的
に説明するが１本発明は下記例に限定されるものではな
い。Next, the present invention will be specifically explained with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the following examples.
前記（１ａ）式で示されるモノメタクリロイルオキシエ
チレンホスフェート１００ｇをアセトンＩＱに室温で撹
拌しながら溶かした後、この溶液に水酸化亜鉛の粉末５
０ｇを加えて２４時間撹拌した。反応終了後、Ｓ濁物を
炉別して取り出し、この懸濁物をアセトン２００ｄで洗
浄して乾燥することにより（１ａ）式の亜鉛塩（本発明
添加剤）１２０ｇを得た。After dissolving 100 g of monomethacryloyloxyethylene phosphate represented by the above formula (1a) in acetone IQ at room temperature with stirring, 55 g of zinc hydroxide powder was added to this solution.
0g was added and stirred for 24 hours. After the reaction was completed, the S suspension was taken out by furnace, and this suspension was washed with 200 d of acetone and dried to obtain 120 g of zinc salt of formula (1a) (additive of the present invention).
また、水酸化亜鉛に代えて水酸化マグネシウム、水酸化
アルミニウム、水酸化カルシウムを使用し。Also, magnesium hydroxide, aluminum hydroxide, and calcium hydroxide are used instead of zinc hydroxide.
同様の方法で（１ａ）式の化合物のマグネシウム塩、ア
ルミニウム塩、カルシウム塩（本発明添加剤）をそれぞ
れ製造した。A magnesium salt, an aluminum salt, and a calcium salt (additive of the present invention) of the compound of formula (1a) were produced in a similar manner.
上記生成物を赤外線吸収スペクトル法及び元素分析法に
よってそれぞれ分析したところ、いずれも目的物である
ことが確認された。When the above products were analyzed by infrared absorption spectroscopy and elemental analysis, it was confirmed that both were the desired products.
第１〜５表に示す組成の実施例１〜２３．比較例１〜１
５のゴムをそれぞれ製造した。この場合、第１．２表は
パーオキサイド加硫系のゴム、第３゜４表は硫黄加硫系
のゴム、第５表はこれら２つの加硫系のゴムを示しであ
る。また、第２表は充填剤配合系のゴムを示しである。Examples 1 to 23 of the compositions shown in Tables 1 to 5. Comparative examples 1-1
No. 5 rubbers were manufactured respectively. In this case, Table 1.2 shows peroxide vulcanized rubber, Table 3.4 shows sulfur vulcanized rubber, and Table 5 shows these two vulcanized rubbers. Furthermore, Table 2 shows rubbers containing fillers.
なお、第１〜５表中実施例はＥ、比較例はＣＥの記号で
表している。In Tables 1 to 5, Examples are represented by E and Comparative Examples are represented by CE.
次に、上記実施例１〜２３、比較例１〜１５のゴムの物
性を調べた。結果を第１〜５表に併記する。なお、引張
試験機はロードセル型試験機を引張速度５００ｍ＋／分
で使用した。また、第２表及び第５表のゴムについては
加硫試験機（キュラストメータ：温度１６０℃、振幅±
３度）を用いて加硫曲線を求めた。結果を第１図及び第
２図に示す。Next, the physical properties of the rubbers of Examples 1 to 23 and Comparative Examples 1 to 15 were examined. The results are also listed in Tables 1-5. As the tensile tester, a load cell type tester was used at a tensile speed of 500 m+/min. In addition, for the rubbers in Tables 2 and 5, a vulcanization tester (curastmeter: temperature 160°C, amplitude ±
3 degrees) to determine the vulcanization curve. The results are shown in Figures 1 and 2.
第１〜５表及び第１，２図の結果より、（１）式の化合
物の亜鉛塩及びマグネシウム塩は、パーオキサイド加硫
系ゴム及び硫黄・促進加硫系ゴムのいずれに対しても改
質効果を有することが認められた。この場合、パーオキ
サイド加硫系では硬度。From the results in Tables 1 to 5 and Figures 1 and 2, the zinc salt and magnesium salt of the compound of formula (1) are effective in modifying both peroxide vulcanized rubber and sulfur/accelerated vulcanization rubber. It was recognized that this had a quality effect. In this case, hardness for peroxide vulcanization systems.
モジュラス、引張強さが改善され、しかもこれら硬度、
モジュラス、引張強さの上昇が大きいわりに伸びの低下
率が小さいという利点があり、（１）式の化合物の塩が
共架橋剤として作用していると思われる。また、（１）
式の化合物の塩の添加量の増大とともに加硫試験機から
得られる加硫曲線の最大トルク値が上昇した。このよう
な改質効果は、ＮＢＲ，ＳＢＲで特に顕著であった。ま
た、硫黄加硫系においては、引張強さ、伸びが大きく上
昇したのに対し、硬度は殆ど変化がなく、初期モジュラ
ス（１００〜３００％程度）は低下した。このような補
強性は例がないので、新規用途に有望であると思われる
。また、このような改質効果はＢＲ，ＳＢＲ，ＮＢＲ，
ＥＰＤＭのいずれにも認められたが、特にＢＲ，ＳＢＲ
で顕著であった。The modulus and tensile strength are improved, and these hardness and
It has the advantage that the decrease in elongation is small in spite of the large increase in modulus and tensile strength, and it is thought that the salt of the compound of formula (1) acts as a co-crosslinking agent. Also, (1)
The maximum torque value of the vulcanization curve obtained from the vulcanization tester increased as the amount of salt of the compound of formula increased. Such a modification effect was particularly remarkable in NBR and SBR. In addition, in the sulfur vulcanization system, the tensile strength and elongation greatly increased, while the hardness hardly changed and the initial modulus (about 100 to 300%) decreased. Since this kind of reinforcing property has never been seen before, it is thought to be promising for new applications. In addition, such a modification effect can be applied to BR, SBR, NBR,
It was recognized in both EPDM, but especially in BR and SBR.
It was noticeable.
この場合、ＳＢＨにおいてはチアゾール（ＤＭ）系、ス
ルフェンアミド（ＣＢＳ）系で引張強さの上昇に特に効
果があった。更に、充填剤配合系においては引張強さ、
引裂強さ、硬度が向上した。In this case, in SBH, thiazole (DM) type and sulfenamide (CBS) type were particularly effective in increasing the tensile strength. Furthermore, in filler-containing systems, tensile strength,
Improved tear strength and hardness.
また、（１）式の化合物の塩の添加により加硫試験機（
キュラストメータ）から得られる加硫曲線のトルク値が
上昇した。それ故１本発明添加剤の応用については、炭
酸カルシウム等の補強性の小さい充填剤との併用が好ま
しいと考えられる。In addition, by adding the salt of the compound of formula (1), the vulcanization tester (
The torque value of the vulcanization curve obtained from the Curelastometer) increased. Therefore, regarding the application of the additive of the present invention, it is considered preferable to use it in combination with a filler having low reinforcing properties such as calcium carbonate.
第１図及び第２図はそれぞれ本発明添加剤を配合したゴ
ムと配合しないゴムの加硫曲線を示すグラフである。FIGS. 1 and 2 are graphs showing the vulcanization curves of rubbers with and without the additives of the present invention, respectively.
Claims (1)
る。） で示される化合物の亜鉛塩、マグネシウム塩、アルミニ
ウム塩又はカルシウム塩からなることを特徴とするゴム
改質用添加剤。[Claims] 1. Represented by the following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, R is a hydrogen atom or a methyl group, and n is 1 or 2.) A rubber-modifying additive characterized by comprising a zinc salt, magnesium salt, aluminum salt, or calcium salt of a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29528589A JPH03157434A (en) | 1989-11-14 | 1989-11-14 | Additive for modifying rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29528589A JPH03157434A (en) | 1989-11-14 | 1989-11-14 | Additive for modifying rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03157434A true JPH03157434A (en) | 1991-07-05 |
Family
ID=17818625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29528589A Pending JPH03157434A (en) | 1989-11-14 | 1989-11-14 | Additive for modifying rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03157434A (en) |
-
1989
- 1989-11-14 JP JP29528589A patent/JPH03157434A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE112008003363B4 (en) | Rubber composition, its use and innerliner | |
| EP0854171B1 (en) | Rubber compositions containing modified rubber gels | |
| KR100841521B1 (en) | Rubber Mixtures Containing Silicic Acid, Soot and Rubber Gel | |
| DE2552617C2 (en) | A method for producing a modified rubbery terpolymer and its use | |
| JP2001089606A (en) | Microgel-containing rubber mixture with mask bifunctional mercaptan and vulcanized product prepared therefrom | |
| JPH04275349A (en) | Vulcanized rubber | |
| DE2933345A1 (en) | VULCANIZABLE RUBBER MIXTURE BASED ON HALOGEN-FREE RUBBER, METHOD FOR VULCANIZING THESE RUBBER MIXTURES AND USE OF THE RUBBER MIXTURES | |
| US6797780B2 (en) | Microgel-containing rubber compounds with phosphoryl polysulfides and vulcanizates or shaped articles prepared therefrom | |
| DE112008003343B4 (en) | Rubber composition for a breaker topcoat | |
| EP2870195B1 (en) | Mélanges de caoutchouc avec acide silique contenant de l'ester w-mercaptocarboxylique d'alcools polyvalents | |
| JP2005060697A (en) | Carbon black having organic group, method for producing the same, rubber compound containing the carbon black, method for producing the compound, use of the compound and molded product comprising the same | |
| EP1148094B1 (en) | Chloroprene-based rubber composition | |
| EP2724870A1 (en) | Polysulphide mixtures, method for their preparation and use of the polysulphide mixtures in rubber mixtures | |
| EP3622015B1 (en) | Rubber compositions containing sulphur-containing organosilicon compounds | |
| JP2017206628A (en) | Rubber composition for tire | |
| KR102167527B1 (en) | Conjugated-diene based copolymer composition, method for preparing the copolymer composition and rubber composition comprising the copolymer composition | |
| JP3690890B2 (en) | Low exothermic rubber composition | |
| US9725562B2 (en) | Modified diene polymer, method for producing same, rubber composition, and pneumatic tire | |
| US4525517A (en) | Vulcanizable polymer compositions with improved scorch | |
| JP2017115112A (en) | Modified diene rubber, rubber composition for tire and manufacturing method therefor | |
| US4604420A (en) | Vulcanizable polymer compositions with improved scorch | |
| JP2013159769A (en) | Rubber composition for tire and pneumatic tire | |
| JPH03157434A (en) | Additive for modifying rubber | |
| US2669592A (en) | Lignin-reinforced rubber | |
| EP0590457B1 (en) | Benzothiazole derivatives as vulcanisation accelerators suitable for the introduction of polar substituents |