JPH04504B2 - - Google Patents
Info
- Publication number
- JPH04504B2 JPH04504B2 JP5499785A JP5499785A JPH04504B2 JP H04504 B2 JPH04504 B2 JP H04504B2 JP 5499785 A JP5499785 A JP 5499785A JP 5499785 A JP5499785 A JP 5499785A JP H04504 B2 JPH04504 B2 JP H04504B2
- Authority
- JP
- Japan
- Prior art keywords
- aging
- weight
- parts
- ethylene
- present
- 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
- 230000003712 anti-aging effect Effects 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- -1 benzimidazole compound Chemical class 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 150000001556 benzimidazoles Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 description 1
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔技術分野〕
本発明は老化防止剤に関し、更に詳しくは有機
高分子物質に対して極めて有効な老化防止剤に関
する。
〔従来技術〕
オレフイン系重合体就中エチレン系重合体は優
れた電気絶縁性を有し、また放射線架橋、有機過
酸化物架橋、シラン化合物を用いる架橋等各種の
架橋手段を適宜に採用して架橋出来惹いては各種
物性を改善出来る利点があるため、従来から電気
絶縁材料を始め、各種の分野に巾広く使用されて
来た。
而して最近電気機器をはじめ、車輌、自動車等
の各分野に於いて絶縁電線就中電子ワイヤーとい
われる絶縁電線のより高度の特性が要求されるよ
うになり、特に従来の老化防止性よりも格段に優
れた老化防止性が強く要望されるようになつて来
た。
〔発明の目的並びにその概要〕
本発明者は従来から上記オレフイン系重合体の
有する上記難点に注目し、耐老化性の著しく優れ
たオレフイン系重合体就中エチレン系重合体組成
物を開発すべく鋭意研究を続けて来たが、この研
究に於いて、ある特定の二種類の化合物を併用し
て老化防止剤として使用するときは、これ等特定
の二種類の化合物の相乗作用により、老化防止性
が著しく顕著に向上することを見出し、またこの
特定の二種類より成る老化防止剤はオレフイン系
重合体には勿論のこと、これ以外の有機高分子物
質に対してもその優れた相乗作用により著しく優
れた老化防止性を発揮することを見出し、これ等
の新しい事実に基づき本発明を完成するに至つ
た。即ち本発明はベンズイミダゾール系化合物
100重量部及び１，３，５−トリス（3′，5′−ジ
−ｔ−ブチル−４−ヒドロキシベンゾイル）イソ
シアヌレート１〜500重量部を含有して成る有機
高分子用老化防止剤に係るものである。
〔発明の効果〕
本発明に於いてはベンズイミダゾール系化合物
及び１，３，５−トリス（3′，5′−ジ−ｔ−ブチ
ル−４−ヒドロキシベンゾイル）イソシアヌレー
ト（以下単にイソシアヌレートという）という特
定の２種類の化合物を上記の如き特定割合で併用
することにより、後記実施例でも示す通り、これ
等２種の化合物の相乗作用により著しく優れた老
化防止性を発揮する。この老化防止性は広く有機
高分子化合物に対して発揮されるが、特にオレフ
イン系重合体に対し顕著に発揮される。また上記
ベンズイミダゾール系化合物とイソシアヌレート
とを併用する際に、更にこれ等以外の窒素または
硫黄原子を含む老化防止性物質を第三成分として
併用することにより、これ等各化合物の相乗作用
により更に老化防止性が一段と優れる効果があ
る。
〔発明の構成〕
本発明は基本的にはベンズイミダゾール系化合
物100重量部及びイソシアヌレート１〜500重量部
とを含有して成る老化防止剤であり、この基本的
老化防止剤に、更に窒素又は硫黄原子を含むその
他の老化防止性物質が第三成分として含有されて
成る老化防止剤である。
本発明に於いて使用されるベンズイミダゾール
系化合物としては、たとえば２−メルカプトベン
ズイミダゾール、その金属たとえば亜鉛塩、２−
メルカプトメチルベンズイミダゾール、その金属
たとえば亜鉛塩、ベンズイミダゾールをその代表
例として例示出来、その他ベンズイミダゾール系
化合物で老化防止性を有するものが含まれる。
本発明のベンズイミダゾール系化合物とイソシ
アヌレートとの割合は前者100重量部に対し後者
１〜500重量部好ましくは２〜200重量部より好ま
しくは５〜100重量部であり、後者が１重量部に
達しないときはこれ等両者の相乗効果が充分に発
揮され難い。
また本発明に於いて第三成分として更に上記二
種の化合物と併用される窒素または硫黄原子を含
有する老化防止性物質はベンズイミダゾール100
重量部に対し１〜100重量部好ましくは５〜20重
量部程度使用される。これ等老化防止性物質とし
てはたとえばジチオプロピオン酸ラウイル、メラ
ミン等を好ましい具体例として挙げることが出来
る。
本発明の老化防止剤は各種の有機高分子物質に
対して使用されるが、オレフイン系重合体に対し
て特に好ましく使用される。この際のオレフイン
系重合体としてはたとえばエチレン、プロピレ
ン、ブチレン、４−メチルペンテン−１等の単独
または共重合体が広く含まれるが、好ましいもの
として、エチレンの単独または共重合体を挙げる
ことが出来る。この際のエチレンの単独重合体と
しては通常のポリエチレンが使用出来るが、より
好ましくは直鎖状で低密度のものであり、たとえ
ば密度0.92ｇ／cm3程度のものを好ましいものとし
て例示出来る。またエチレンの共重合体としては
エチレンと共重合しうる他の単量体との共重合体
が例示出来、たとえばエチレン−酢酸ビニル共重
合体（以下EVAという）、エチレン−エチルアク
リレート共重合体（以下EEAという）、エチレン
−プロピレン共重合体、エチレン−プロピレン−
ジエン共重合体等を挙げることが出来る。
本発明老化防止剤の使用量は、使用する有機高
分子物質の種類、その用途等により異なるが、通
常有機高分子物質100重量部に対し本発明老化防
止剤を0.5〜20重量部好ましくは１〜10重量部使
用する。
本発明組成物は更に必要に応じてその他の他の
通常の各種添加剤を添加することが出来る。この
際の他の添加剤としては、たとえばその他の難燃
剤、各種老化防止剤、無機充填剤等があり、また
架橋材、架橋助材等も使用することが出来る。
以下に実施例を示して本発明をより具体的に説
明する。但し下記例に於いて部とあるは重量部を
示すものとする。
実施例 １
第１表並びに第２表に示す所定の配合割合で充
分混練して組成物を調製した。この組成物につい
て耐熱老化性と銅存在下の老化性を夫々測定し
た。この結果を第３表に示す。但し照射架橋を行
なつたものについては、その架橋は電子線速器に
て20Mradで架橋した。
＜耐熱老化性＞
組成物を厚さ１mmにプレスシート化し、これを
JIS Ｋ 6723に従つて加熱劣化し、伸びの絶対値
が50％となるときの劣化日数を測定した。
＜銅害存在下の老化性＞
組成物を常法に従つて銅線に被覆して電線とな
し、この電線を所定の高温に曝露して老化した
後、室温で自己径巻付によつてクラツクが発生す
る時間を測定した。
但し第１表中で重合体として使用した各種重合
体は夫々次のものを示す。
LLDPE−１（直鎖状ポリエチレン）：密度 0.925
メルトインデツクス（以下M.I.という） 1.0
LLDPE−２（直鎖状ポリエチレン）：密度 0.925
M.I. 4.0
EVA−１：酢酸ビニル（以下EVという）含量
15wt％
M.I. 0.5
EVA−２：EV含量10wt％
M.I. 1.0
EEA−１：エチルアクリレート（EAという）含
量15wt％
M.I. 1.5
EEA−２：EA含量15wt％
M.I. 0.5
P.P（ポリプロピレン）：密度0.90
M.I. 1.2
ポリ−４−メチルペンテン−１：密度0.835
：M.I. 1.26
（260℃、５Kg）
[Technical Field] The present invention relates to anti-aging agents, and more particularly to anti-aging agents that are extremely effective against organic polymeric substances. [Prior art] Olefin polymers, especially ethylene polymers, have excellent electrical insulation properties, and various crosslinking methods such as radiation crosslinking, organic peroxide crosslinking, and crosslinking using silane compounds can be appropriately employed. Since crosslinking has the advantage of improving various physical properties, it has been widely used in various fields including electrical insulation materials. Recently, in various fields such as electrical equipment, vehicles, and automobiles, insulated wires, especially electronic wires, have been required to have more advanced properties, especially those with higher anti-aging properties than conventional ones. There has been a strong demand for significantly superior anti-aging properties. [Object of the Invention and Summary thereof] The present inventor has paid attention to the above-mentioned drawbacks of the above-mentioned olefin-based polymers, and has set out to develop an olefin-based polymer composition, particularly an ethylene-based polymer composition, which has extremely excellent aging resistance. We have been conducting intensive research, and in this research, we found that when two specific compounds are used together as an anti-aging agent, the synergistic effect of these two specific compounds causes anti-aging effects. We have discovered that this particular two-type anti-aging agent has an excellent synergistic effect not only on olefinic polymers but also on other organic polymers. It was discovered that it exhibits extremely excellent anti-aging properties, and based on these new facts, the present invention was completed. That is, the present invention relates to benzimidazole compounds.
Relating to an antiaging agent for organic polymers comprising 100 parts by weight of 1-500 parts by weight of 1,3,5-tris(3',5'-di-t-butyl-4-hydroxybenzoyl)isocyanurate. It is something. [Effects of the Invention] In the present invention, benzimidazole compounds and 1,3,5-tris(3',5'-di-t-butyl-4-hydroxybenzoyl)isocyanurate (hereinafter simply referred to as isocyanurate) are used. By using two specific types of compounds in combination in the above-mentioned specific ratios, extremely excellent anti-aging properties are exhibited due to the synergistic action of these two types of compounds, as shown in the examples below. This anti-aging property is exhibited by a wide range of organic polymer compounds, but is particularly noticeable by olefinic polymers. Furthermore, when using the above-mentioned benzimidazole compound and isocyanurate in combination, by further using an anti-aging substance containing nitrogen or sulfur atoms as a third component, the synergistic effect of each of these compounds will result in an even greater effect. It has an even better anti-aging effect. [Structure of the Invention] The present invention is basically an anti-aging agent containing 100 parts by weight of a benzimidazole compound and 1 to 500 parts by weight of an isocyanurate, and this basic anti-aging agent further contains nitrogen or This anti-aging agent contains another anti-aging substance containing a sulfur atom as a third component. Examples of the benzimidazole compounds used in the present invention include 2-mercaptobenzimidazole, its metal salt such as zinc salt, 2-mercaptobenzimidazole,
Typical examples include mercaptomethylbenzimidazole, its metals such as zinc salts, and benzimidazole, and other benzimidazole compounds having anti-aging properties. The proportion of the benzimidazole compound of the present invention and isocyanurate is 1 to 500 parts by weight, preferably 2 to 200 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the former, and 1 part by weight of the latter. If this is not achieved, it is difficult for the synergistic effect of the two to be fully exhibited. Further, in the present invention, the anti-aging substance containing nitrogen or sulfur atoms which is further used as a third component in combination with the above two types of compounds is benzimidazole 100.
The amount used is about 1 to 100 parts by weight, preferably about 5 to 20 parts by weight. Preferred specific examples of these anti-aging substances include layl dithiopropionate and melamine. The anti-aging agent of the present invention can be used for various organic polymer substances, but is particularly preferably used for olefinic polymers. In this case, the olefin polymers include a wide range of homopolymers or copolymers of ethylene, propylene, butylene, 4-methylpentene-1, etc., but ethylene homopolymers or copolymers are preferred. I can do it. As the ethylene homopolymer in this case, ordinary polyethylene can be used, but it is more preferably linear and low density, for example, one with a density of about 0.92 g/cm 3 is preferred. Examples of copolymers of ethylene include copolymers with other monomers that can be copolymerized with ethylene, such as ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) and ethylene-ethyl acrylate copolymer (hereinafter referred to as EVA). (hereinafter referred to as EEA), ethylene-propylene copolymer, ethylene-propylene-
Examples include diene copolymers and the like. The amount of the anti-aging agent of the present invention to be used varies depending on the type of organic polymer substance used, its use, etc., but usually 0.5 to 20 parts by weight of the anti-aging agent of the present invention is preferably 1 part by weight per 100 parts by weight of the organic polymer substance. ~10 parts by weight are used. The composition of the present invention may further contain various other conventional additives, if necessary. Examples of other additives in this case include other flame retardants, various anti-aging agents, inorganic fillers, etc., and crosslinking agents, crosslinking aids, etc. can also be used. EXAMPLES The present invention will be explained in more detail with reference to Examples below. However, in the following examples, parts refer to parts by weight. Example 1 A composition was prepared by sufficiently kneading the mixture at the predetermined mixing ratios shown in Tables 1 and 2. The heat aging resistance and the aging resistance in the presence of copper of this composition were measured. The results are shown in Table 3. However, for those subjected to irradiation crosslinking, the crosslinking was carried out at 20 Mrad using an electron beam analyzer. <Heat aging resistance> The composition was made into a press sheet with a thickness of 1 mm, and this was
Heat deterioration was performed according to JIS K 6723, and the number of days of deterioration when the absolute value of elongation reached 50% was measured. <Aging properties in the presence of copper damage> A copper wire is coated with the composition according to a conventional method to form an electric wire, and after aging by exposing the electric wire to a predetermined high temperature, the composition is coated with the composition by self-diameter winding at room temperature. The time required for the crack to occur was measured. However, the various polymers used as polymers in Table 1 are shown below. LLDPE-1 (linear polyethylene): Density 0.925 Melt index (hereinafter referred to as MI) 1.0 LLDPE-2 (linear polyethylene): Density 0.925 MI 4.0 EVA-1: Vinyl acetate (hereinafter referred to as EV) content
15wt% MI 0.5 EVA-2: EV content 10wt% MI 1.0 EEA-1: Ethyl acrylate (referred to as EA) content 15wt% MI 1.5 EEA-2: EA content 15wt% MI 0.5 PP (polypropylene): Density 0.90 MI 1.2 Poly- 4-Methylpentene-1: Density 0.835: MI 1.26 (260℃, 5Kg)
【表】【table】
【表】【table】
Claims (1)
１，３，５−トリス（3′，5′−ジ−ｔ−ブチル−
４−ヒドロキシベンゾイル）イソシアヌレート１
〜500重量部を含有して成るオレフイン系重合体
用老化防止剤。1 100 parts by weight of a benzimidazole compound and 1,3,5-tris(3',5'-di-t-butyl-
4-Hydroxybenzoyl)isocyanurate 1
~500 parts by weight of an antiaging agent for olefinic polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5499785A JPS61213266A (en) | 1985-03-19 | 1985-03-19 | Antioxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5499785A JPS61213266A (en) | 1985-03-19 | 1985-03-19 | Antioxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61213266A JPS61213266A (en) | 1986-09-22 |
| JPH04504B2 true JPH04504B2 (en) | 1992-01-07 |
Family
ID=12986295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5499785A Granted JPS61213266A (en) | 1985-03-19 | 1985-03-19 | Antioxidant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61213266A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63207837A (en) * | 1987-02-25 | 1988-08-29 | Idemitsu Petrochem Co Ltd | Polyethylene resin composition |
-
1985
- 1985-03-19 JP JP5499785A patent/JPS61213266A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61213266A (en) | 1986-09-22 |
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