JP2554657B2 - Flame retardant chlorine polyethylene composition - Google Patents
Flame retardant chlorine polyethylene compositionInfo
- Publication number
- JP2554657B2 JP2554657B2 JP14389487A JP14389487A JP2554657B2 JP 2554657 B2 JP2554657 B2 JP 2554657B2 JP 14389487 A JP14389487 A JP 14389487A JP 14389487 A JP14389487 A JP 14389487A JP 2554657 B2 JP2554657 B2 JP 2554657B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- chlorinated polyethylene
- composition
- polyethylene composition
- 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
- 239000000203 mixture Substances 0.000 title claims description 21
- -1 polyethylene Polymers 0.000 title claims description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052801 chlorine Inorganic materials 0.000 title claims description 8
- 239000000460 chlorine Substances 0.000 title claims description 8
- 239000003063 flame retardant Substances 0.000 title claims description 8
- 229920000573 polyethylene Polymers 0.000 title claims description 4
- 239000004698 Polyethylene Substances 0.000 title description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 150000003568 thioethers Chemical class 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- UKWUOTZGXIZAJC-UHFFFAOYSA-N 4-nitrosalicylic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1O UKWUOTZGXIZAJC-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は耐熱性の改良された塩素化ポリエチレン組
成物に係り、特にモータ口出し線シース材料として好適
に用いられる難燃性塩素化ポリエチレン組成物に関す
る。Description: TECHNICAL FIELD The present invention relates to a chlorinated polyethylene composition having improved heat resistance, and in particular, a flame-retardant chlorinated polyethylene composition suitable for use as a motor lead wire sheath material. Regarding
［従来の技術及び発明が解決しようとする問題点］ 従来、モータの口出線用シース材料としては主として
耐熱温度105℃（CL、CSA規定）の塩素化ポリエチレン組
成物が使用されている。しかし、最近の機器の大容量化
等に伴いモータの耐熱性向上の要求は大きく、それに伴
って口出線に従来以上の耐熱性が要求される。耐熱温度
105℃以上の耐熱性組成物としてはシリコーン組成物が
あるが、シリコーン組成物は高価で、しかも塩素化ポリ
エチレンに比べ機械的強度及び可撓性が劣り、機械的強
度、可撓性の要求される口出線用材料として適当でな
い。[Prior Art and Problems to be Solved by the Invention] Conventionally, a chlorinated polyethylene composition having a heat-resistant temperature of 105 ° C. (CL, CSA standard) has been mainly used as a sheath material for a lead wire of a motor. However, there is a great demand for improving the heat resistance of the motor with the recent increase in the capacity of equipment, and accordingly, the heat resistance of the lead wire is required to be higher than before. Heatproof temperature
There is a silicone composition as a heat-resistant composition having a temperature of 105 ° C or higher, but the silicone composition is expensive and inferior in mechanical strength and flexibility to chlorinated polyethylene. Not suitable as a lead wire material.
本発明はこのような従来の問題点を解決し、塩素化ポ
リエチレン組成物を改質することにより機械的強度及び
可撓性に優れ且つ耐熱温度の高い難燃性塩素化ポリエチ
レン組成物を提供せんとするものである。The present invention solves such conventional problems and does not provide a flame-retardant chlorinated polyethylene composition having excellent mechanical strength and flexibility and high heat resistance by modifying the chlorinated polyethylene composition. It is what
［問題点を解決するための手段］ このような目的を達成する本発明の難燃性塩素化ポリ
エチレン組成物は、塩素含有量が15重量％〜40重量％で
ある塩素化ポリエチレン50重量部〜90重量部とエチレン
系共重合体50重量部〜10重量部とからなる組成物100重
量部に対し熱安定剤としてBa−Zn系複合脂肪酸塩１重量
部〜15重量部及びチオエーテル系酸化防止剤0.1重量部
〜５重量部を添加したことを特徴とする。[Means for Solving the Problems] The flame-retardant chlorinated polyethylene composition of the present invention which achieves such an object is 50 parts by weight of chlorinated polyethylene having a chlorine content of 15% by weight to 40% by weight. 100 parts by weight of a composition consisting of 90 parts by weight and 50 parts by weight to 10 parts by weight of an ethylene copolymer, 1 to 15 parts by weight of a Ba-Zn complex fatty acid salt as a heat stabilizer, and a thioether antioxidant. It is characterized in that 0.1 to 5 parts by weight is added.
ここで、塩素化ポリエチレンは、塩素含有量が15重量
％〜40重量％、好ましくは30重量％〜35重量％のものを
用いる。塩素含有量が15重量％以下では柔軟性及び難燃
性が劣り、また40重量％より多い場合は加工性が悪い。The chlorinated polyethylene used herein has a chlorine content of 15% by weight to 40% by weight, preferably 30% by weight to 35% by weight. When the chlorine content is 15% by weight or less, flexibility and flame retardancy are poor, and when it is more than 40% by weight, workability is poor.
エチレン系共重合体としてはエチレン−酢酸ビニル共
重合体、エチレン−アクリル酸エチル共重合体等が用い
られる。As the ethylene-based copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like are used.
塩素化ポリエチレンとエチレン系共重合体との配合比
は塩素化ポリエチレン50重量部〜90重量部に対しエチレ
ン系共重合体50重量部〜10重量部とする。塩素化ポリエ
チレンが50重量部以下では難燃性が悪く、90重量部以上
では耐熱性が劣る。The mixing ratio of chlorinated polyethylene and ethylene copolymer is 50 to 90 parts by weight of chlorinated polyethylene and 50 to 10 parts by weight of ethylene copolymer. If the amount of chlorinated polyethylene is 50 parts by weight or less, the flame retardancy is poor, and if it is 90 parts by weight or more, the heat resistance is poor.
本発明においては上記塩素化ポリエチレンとエチレン
系共重合体とから成る組成物に対し、耐熱性を向上させ
る目的でBa−Zn系複合脂肪酸塩及びチオエーテル系酸化
防止剤が添加される。Ba−Zn系複合脂肪酸塩及びチオエ
ーテル系酸化防止剤はそれぞれ熱安定剤、酸化防止剤と
して公知のものであるが、これらを組み合わせて用いる
ことにより優れた耐熱性、特に熱老化に対する耐性が得
られる。本発明におけるBa−Za系複合脂肪酸塩とは、バ
リウム系脂肪酸塩と亜鉛系脂肪酸塩との混合物であっ
て、バリウム系脂肪酸塩としてはステアリン酸バリウ
ム、ラウリン酸バリウムが好ましく、亜鉛系脂肪酸塩と
してはステアリン酸亜鉛、ラウリン酸亜鉛が好ましく、
これらのバリウム系脂肪酸塩と、亜鉛系脂肪酸塩とをそ
れぞれ１種以上任意に組合わせて使用される。バリウム
系脂肪酸塩と、亜鉛系脂肪酸塩の混合比としては1:1〜
0.7:0.3が好ましい。このようなBa−Zn系複合脂肪酸は
上記塩素化ポリエチレン組成物100重量部に対し、１重
量部〜15重量部用いられる。１重量部以下では耐熱性の
向上が見られず、15重量部以上では加工性が低下し且つ
製品の表面に安定剤が吹き出る、いわゆるブルーミング
を生じる。In the present invention, a Ba—Zn complex fatty acid salt and a thioether antioxidant are added to the composition comprising the chlorinated polyethylene and the ethylene copolymer in order to improve heat resistance. Ba-Zn-based complex fatty acid salts and thioether-based antioxidants are known as heat stabilizers and antioxidants, respectively, but by using them in combination, excellent heat resistance, particularly resistance to heat aging, can be obtained. . The Ba-Za-based complex fatty acid salt in the present invention is a mixture of a barium-based fatty acid salt and a zinc-based fatty acid salt, and as the barium-based fatty acid salt, barium stearate or barium laurate is preferable, and the zinc-based fatty acid salt is used. Is preferably zinc stearate or zinc laurate,
These barium-based fatty acid salts and zinc-based fatty acid salts may be used in any combination of one or more. The mixing ratio of barium fatty acid salt and zinc fatty acid salt is 1: 1 ~
0.7: 0.3 is preferable. Such a Ba-Zn complex fatty acid is used in an amount of 1 to 15 parts by weight per 100 parts by weight of the chlorinated polyethylene composition. If it is less than 1 part by weight, the heat resistance is not improved, and if it is more than 15 parts by weight, the workability is lowered and the stabilizer blows out on the surface of the product, so-called blooming occurs.
チオエーテル系酸化防止剤は ここで、ＲはC12〜C14のアルキルを示す。Thioether antioxidant Here, R represents C 12 -C 14 alkyl.
ここで、ＲはC13のアルキルを示す。 Here, R represents C 13 alkyl.
等の構造式で表されるものが好適に使用される。チオエ
ーテル系酸化防止剤の添加量は塩素化ポリエチレン組成
物100重量部に対し、0.1重量部〜５重量部とする。0.1
重量部以下では耐熱性が劣り、５重量部以上では架橋特
性が低下する。 Those represented by structural formulas such as are preferably used. The amount of the thioether antioxidant added is 0.1 to 5 parts by weight based on 100 parts by weight of the chlorinated polyethylene composition. 0.1
If it is less than 5 parts by weight, the heat resistance will be inferior, and if it is more than 5 parts by weight, the crosslinking property will be deteriorated.
本発明の難燃性塩素化ポリエチレン組成物は以上説明
した成分の他、難燃性を向上する目的で、三酸化アンチ
モン、五酸化アンチモン等の金属酸化物及び／又は臭素
系、塩素系などの有機難燃剤を添加することが好まし
い。その他、焼成クレーなどの公知の充填剤、安定剤等
を添加することができる。また、架橋方法に応じて適宜
架橋剤、架橋助剤を添加する。架橋方法は、電離性放射
線の照射、過酸化物添加による蒸気架橋、シラングラフ
トさせる水架橋などを任意に選ぶことができる。本発明
の組成物を口出線用シースとして用いるにはロールミ
ル、バンバリーミキサーなどによる樹脂温120℃前後で
混練し、ペレット化した後、押出温度90℃〜100℃で押
出機により押出しながら所望のケーブルのシースとして
成型し、架橋させる。In addition to the components described above, the flame-retardant chlorinated polyethylene composition of the present invention has a metal oxide such as antimony trioxide or antimony pentoxide and / or a bromine-based or chlorine-based compound for the purpose of improving flame retardancy. It is preferable to add an organic flame retardant. In addition, known fillers such as calcined clay and stabilizers may be added. Further, a cross-linking agent and a cross-linking aid are appropriately added depending on the cross-linking method. As the crosslinking method, irradiation of ionizing radiation, vapor crosslinking by addition of peroxide, water crosslinking by silane grafting and the like can be arbitrarily selected. In order to use the composition of the present invention as a sheath for a lead wire, a kneading is performed at a resin temperature of about 120 ° C. by a roll mill, a Banbury mixer, etc., and after pelletization, a desired extruding temperature of 90 ° C. to 100 ° C. is extruded by an extruder. Molded as a cable sheath and crosslinked.
［実施例］ 塩素化ポリエチレンとして、塩素量30重量％のもの又
は塩素量40重量％のものを、ポリエチレン系共重合体と
してエチレン−酢酸ビニル共重合体（EVA）又はエチレ
ン−アクリル酸エチル共重合体（EEA A170）を用い、Ba
−Za系複合脂肪酸塩としてステアリン酸バリウム及びス
テアリン酸亜鉛を0.7:0.3の割合で混合したもの使用
し、チオエーテル系酸化防止剤として構造式（１）で示
されるものを使用し、表１に示す配合比（実施例１〜
４）で製造した成型品について引張強度及び伸び、熱老
化（158℃で７日間放置後の引張強度及び伸びの残存
率）、難燃性（酸素指数）、及び柔軟性を試験した。[Example] A chlorinated polyethylene having a chlorine content of 30% by weight or a chlorine content of 40% by weight, and a polyethylene copolymer having an ethylene-vinyl acetate copolymer (EVA) or an ethylene-ethyl acrylate copolymer Using combined (EEA A170), Ba
As the -Za-based complex fatty acid salt, barium stearate and zinc stearate mixed in a ratio of 0.7: 0.3 are used, and as the thioether-based antioxidant, the one represented by the structural formula (1) is used. Mixing ratio (Examples 1 to 1
The molded product produced in 4) was tested for tensile strength and elongation, heat aging (residual ratio of tensile strength and elongation after standing at 158 ° C. for 7 days), flame retardancy (oxygen index), and flexibility.
［比較例］ 塩素化ポリエチレンとポリエチレン系共重合体との配
合比を30:70（重量比）とし、それら以外の成分は実施
例４と同じ配合量としたもの（比較例１、２）、実施例
１と同成分で但し、安定剤としてBa−Zn系安定剤を用い
ず三塩基性硫酸鉛を用いたもの（比較例３）及び酸化防
止剤としてチオエーテル系酸化防止剤を用いずフェノー
ル系酸化防止剤を用いたもの（比較例４）のそれぞれに
ついて、実施例と同様の試験を行なった結果を実施例、
比較例共に表２に示す。[Comparative Example] The compounding ratio of the chlorinated polyethylene and the polyethylene-based copolymer was 30:70 (weight ratio), and the other components were the same compounding amount as in Example 4 (Comparative Examples 1 and 2). The same components as in Example 1, except that Ba—Zn stabilizer was not used as a stabilizer and lead tribasic sulfate was used (Comparative Example 3), and a thioether antioxidant was not used as an antioxidant and a phenol type was used. For each of those using the antioxidant (Comparative Example 4), the results of the same test as in the Examples were conducted.
Both comparative examples are shown in Table 2.
［発明の効果］ 以上の結果からも明らかなように本発明の難燃性塩素
化ポリエチレン組成物においてはBa−Zn系安定剤と、チ
オエーテル系酸化防止剤の併用によって耐熱性（熱老
化）が大幅に改善され、しかも機械的強度、柔軟性共に
優れているので、モータ口出し線シース材料等の材料と
して有用である。 [Effect of the invention] As is clear from the above results, in the flame-retardant chlorinated polyethylene composition of the present invention, the heat resistance (heat aging) is improved by the combined use of the Ba-Zn stabilizer and the thioether antioxidant. Since it is greatly improved and has excellent mechanical strength and flexibility, it is useful as a material such as a motor lead wire sheath material.
Claims (1)
素化ポリエチレン50重量部〜90重量部とエチレン系重合
体50重量部〜10重量部とからなる組成物100重量部に対
し、熱安定剤としてBa−Zn系複合脂肪酸塩１重量部〜15
重量部及びチオエーテル系酸化防止剤0.1重量部〜５重
量部を添加したことを特徴とする難燃性塩素化ポリエチ
レン組成物。1. A composition comprising 100 parts by weight of a composition comprising 50 parts by weight to 90 parts by weight of chlorinated polyethylene having a chlorine content of 15% by weight to 40% by weight and 50 parts by weight to 10 parts by weight of an ethylene polymer. , 1 to 15 parts by weight of Ba-Zn complex fatty acid salt as a heat stabilizer
A flame-retardant chlorinated polyethylene composition, characterized in that 0.1 part by weight to 5 parts by weight of a thioether antioxidant is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14389487A JP2554657B2 (en) | 1987-06-09 | 1987-06-09 | Flame retardant chlorine polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14389487A JP2554657B2 (en) | 1987-06-09 | 1987-06-09 | Flame retardant chlorine polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63308054A JPS63308054A (en) | 1988-12-15 |
| JP2554657B2 true JP2554657B2 (en) | 1996-11-13 |
Family
ID=15349520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14389487A Expired - Lifetime JP2554657B2 (en) | 1987-06-09 | 1987-06-09 | Flame retardant chlorine polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2554657B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130203939A1 (en) * | 2010-05-21 | 2013-08-08 | Shuwen Peng | Thermoplastic compositions and articles formed from the same |
| JP2013018935A (en) * | 2011-07-14 | 2013-01-31 | Sumitomo Electric Ind Ltd | Flame-retardant, flexible resin composition, resin tube, and insulated wire using the same |
| JP2016222875A (en) * | 2015-06-03 | 2016-12-28 | 日立金属株式会社 | Elastomer composition and cable |
-
1987
- 1987-06-09 JP JP14389487A patent/JP2554657B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63308054A (en) | 1988-12-15 |
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