JPS6241613B2 - - Google Patents
Info
- Publication number
- JPS6241613B2 JPS6241613B2 JP57069317A JP6931782A JPS6241613B2 JP S6241613 B2 JPS6241613 B2 JP S6241613B2 JP 57069317 A JP57069317 A JP 57069317A JP 6931782 A JP6931782 A JP 6931782A JP S6241613 B2 JPS6241613 B2 JP S6241613B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl chloride
- flame
- polyethylene
- vinyl acetate
- flame retardancy
- 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
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- -1 polyethylene Polymers 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 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 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Description
本発明はポリ塩化ビニル組成物に係り、特に、
燃焼時に強固な発泡炭化層を形成するポリ塩化ビ
ニル組成物に関するものである。
絶縁電線の絶縁体としては、周知のように電気
的性質、耐水性、耐寒性に優れ、加工が容易なポ
リエチレンが広く使用されている。
しかし、ポリエチレンは易燃性であるため、火
災に対する安全性に欠けている。従つて、この易
燃性を改良するために、絶縁体のポリエチレンに
難燃性を付与する試みが種々行なわれている。
ポリエチレンに塩化ポリエチレンのような含塩
素樹脂を混合したり、三酸化アンチモン、塩素化
パラフインを混合することによつて、難燃性を付
与する方法はよく知られているが、この方法によ
れば、ポリエチレン本来の優れた電気的特性を損
なうことが多い。
従つて、絶縁電線に難燃性を付与する方法とし
ては、シース材料の防炎性を強化する方法が望ま
しい。一般の絶縁電線においては、シース材料の
実用上の要求特性、加工性、可撓性等を考慮し
て、主に可塑化ポリ塩化ビニルが使用されてい
る。ポリ塩化ビニル自体は自消性があるが、可撓
性の必要から20〜40重量％の可塑剤を混合すると
燃焼し易くなる。可塑化ポリ塩化ビニルの難燃性
向上対策としては塩素化パラフイン、りん系有機
化合物を三酸化アンチモンと共に混合する方法が
知られており、これによれば良好な難燃性が得ら
れることも周知である。しかし、絶縁体としてポ
リエチレンを使用している絶縁電線の場合には、
このような物質を混合しても十分な難燃性を与え
るシース材料とはなり得ない。絶縁電線の難燃性
の評価にはIEEE―383に記載された難燃性試験
方法が採用される。この方法の大要は、垂直に保
持した絶縁電線にガスバーナの炎を20分間当て、
延焼距離と残炎とを観察するものである。この試
験方法により上記の従来の可塑化ポリ塩化ビニル
で被覆した絶縁電線を試験すると、シース材料が
接炎により燃焼して消失するか、または、亀裂が
生じて、内部絶縁体のポリエチレンに着火して延
焼してしまう。
本発明は上記に鑑みなされたもので、その目的
は、難燃性を有し、接炎時に強固な発泡炭化層を
形成するポリ塩化ビニル組成物を提供することに
ある。
本発明は、ポリ塩化ビニル100重量部に対し
て、酢酸ビニル含有量が15％以上のエチレン―酢
酸ビニル共重合体を少なくとも30重量部混合し、
これに亜鉛化合物の少なくとも一種類、および、
アンチモン、モリブテン、けい素、アルミニウ
ム、マグネシウム、カルシウムそれぞれの酸化
物、水酸化物あるいは炭酸塩のうちの少なくとも
一種類を添加してなることを特徴とするものであ
る。
エチレン―酢酸ビニル共重合体は接炎時の昇温
により軟化溶融する性質をもつており、これに、
燃焼時に発生するガスが発泡剤として作用し、発
泡体を生成させる。ポリ塩化ビニルは燃焼時に炭
化し易い性質があるが、これに亜鉛化合物を併用
すると塩化亜鉛が生成し、これが脱塩化水素の作
用を促進してより炭化性を向上させ、強固な発泡
炭化層が得られる。
エチレン―酢酸ビニル共重合体としては、ポリ
塩化ビニルとの相溶性や燃焼時の発泡性から酢酸
ビニル含有量が15％以上のものが望ましい。その
添加量を30重量部以上としたのは、これ以下では
発泡性に効果がないためである。また、亜鉛化合
物としては、特に、炭酸亜鉛、ほう酸亜鉛、ピロ
メリツト酸亜鉛が好ましく、これらは優れた炭化
触媒として作用する。なお、亜鉛化合物の添加
は、一種類でも効果が認められるが、二種類以上
併用するようにしても同様の効果がある。
さらに、上記の混合物に、アンチモン、モリブ
テン、けい素、アルミニウム、マグネシウム、カ
ルシウムそれぞれの酸化物、水酸化物、あるいは
炭酸塩のうち少なくとも一種類を混合するように
した。このようにすると、発泡炭化層をより強固
にすることができる。なお、他の安定剤、充填
剤、酸化防止剤、着色剤等の配合剤を混合しても
よい。
また、上記のようにして作られた組成物に遊離
基発生剤と多官能モノマとを加えて、熱により架
橋するか、あるいは、多官能モノマを加えてエネ
ルギーリツチ線を照射して架橋することは、耐熱
変形性、耐薬品性を向上できて有効である。
次に、本発明の実施例を比較例とともに第１表
に示し、その効果を第２表に示す。
The present invention relates to polyvinyl chloride compositions, in particular:
The present invention relates to a polyvinyl chloride composition that forms a strong foamed carbonized layer upon combustion. As is well known, polyethylene is widely used as an insulator for insulated wires because it has excellent electrical properties, water resistance, cold resistance, and is easy to process. However, since polyethylene is easily flammable, it lacks fire safety. Therefore, in order to improve this flammability, various attempts have been made to impart flame retardancy to polyethylene as an insulator. It is well known that flame retardancy can be imparted to polyethylene by mixing a chlorinated resin such as chlorinated polyethylene, or by mixing antimony trioxide or chlorinated paraffin. , often impairing the excellent electrical properties inherent to polyethylene. Therefore, as a method of imparting flame retardancy to an insulated wire, a method of strengthening the flame retardance of the sheath material is desirable. In general insulated wires, plasticized polyvinyl chloride is mainly used in consideration of the practically required properties, workability, flexibility, etc. of the sheath material. Although polyvinyl chloride itself is self-extinguishing, it becomes more combustible when 20 to 40% by weight of plasticizer is mixed in to make it flexible. A known method for improving the flame retardancy of plasticized polyvinyl chloride is to mix chlorinated paraffin and phosphorous organic compounds with antimony trioxide, and it is well known that good flame retardancy can be obtained by this method. It is. However, in the case of insulated wires that use polyethylene as the insulator,
Even if such substances are mixed, the sheath material cannot provide sufficient flame retardancy. The flame retardancy test method described in IEEE-383 is used to evaluate the flame retardancy of insulated wires. The gist of this method is to expose an insulated wire held vertically to the flame of a gas burner for 20 minutes.
This is to observe the distance of fire spread and afterflame. When an insulated wire coated with the conventional plasticized polyvinyl chloride described above is tested using this test method, the sheath material either burns and disappears due to contact with the flame, or cracks form and the internal polyethylene insulator ignites. The fire spreads. The present invention has been made in view of the above, and an object thereof is to provide a polyvinyl chloride composition that has flame retardancy and forms a strong foamed carbonized layer when exposed to flame. In the present invention, at least 30 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% or more is mixed with 100 parts by weight of polyvinyl chloride,
At least one type of zinc compound, and
It is characterized by adding at least one of the oxides, hydroxides, or carbonates of antimony, molybdenum, silicon, aluminum, magnesium, and calcium. Ethylene-vinyl acetate copolymer has the property of softening and melting when exposed to flame, and
The gas generated during combustion acts as a blowing agent and produces foam. Polyvinyl chloride has the property of being easily carbonized when burned, but when it is combined with a zinc compound, zinc chloride is generated, which promotes the action of dehydrochlorination and further improves carbonization, creating a strong foamed carbonized layer. can get. The ethylene-vinyl acetate copolymer preferably has a vinyl acetate content of 15% or more from the viewpoint of compatibility with polyvinyl chloride and foamability during combustion. The reason why the amount added is set to 30 parts by weight or more is because if it is less than this, there is no effect on foaming properties. Further, as the zinc compound, zinc carbonate, zinc borate, and zinc pyromellitate are particularly preferred, and these act as excellent carbonization catalysts. It should be noted that although the effect is recognized even when one type of zinc compound is added, the same effect can be obtained even when two or more types are used in combination. Furthermore, at least one kind of oxide, hydroxide, or carbonate of each of antimony, molybdenum, silicon, aluminum, magnesium, and calcium was mixed into the above mixture. In this way, the foamed carbonized layer can be made stronger. In addition, other compounding agents such as stabilizers, fillers, antioxidants, and colorants may be mixed. Alternatively, a free radical generator and a polyfunctional monomer may be added to the composition prepared as described above and crosslinked by heat, or a polyfunctional monomer may be added and crosslinked by irradiation with energy rich radiation. is effective in improving heat deformation resistance and chemical resistance. Next, Table 1 shows examples of the present invention along with comparative examples, and Table 2 shows the effects thereof.
【表】【table】
【表】【table】
【表】
上記燃焼試験は、38mm2の導体に、絶縁体として
ポリエチレンを厚さ1.5mm被覆したコア上に、本
発明になる難燃性組成物をシース材料として1.5
mmの厚さになるように被覆したものを、IEEE―
383燃焼試験に準拠して行なつた。
その結果は上記のように、本発明に係る難燃性
のポリ塩化ビニル組成物をシース材料とすれば、
燃焼試験に良好な結果を示し、絶縁電線例えば、
コントロールケーブル、高電圧ケーブル等を難燃
化するためのシースとして好適である。
なお、実施例１〜５に示す難燃性組成物を溶融
加工し、これをテープ状にして粘着剤を塗布すれ
ば、延焼防止用テープとして用いることができ
る。さらに、チユーブ、パイプ等にも応用でき
る。
以上説明したように、本発明のポリ塩化ビニル
組成物は難燃性であり、燃焼時に発泡して強固な
炭化層を形成するものであるため、特に、絶縁電
線に用いてすぐれた実用的効果を奏することがで
きる。[Table] The above combustion test was conducted using the flame retardant composition of the present invention as a sheath material on a core of a 38 mm 2 conductor coated with polyethylene as an insulator to a thickness of 1.5 mm.
IEEE-
383 combustion test. As mentioned above, the results show that if the flame-retardant polyvinyl chloride composition of the present invention is used as a sheath material,
Showing good results in combustion tests, insulated wires e.g.
It is suitable as a sheath for making control cables, high voltage cables, etc. flame retardant. In addition, if the flame retardant compositions shown in Examples 1 to 5 are melt-processed, made into a tape shape, and coated with an adhesive, it can be used as a tape for preventing the spread of fire. Furthermore, it can be applied to tubes, pipes, etc. As explained above, the polyvinyl chloride composition of the present invention is flame retardant and foams to form a strong carbonized layer when burned, so it has excellent practical effects especially when used for insulated wires. can be played.
Claims (1)
ニル含有量が15％以上のエチレン―酢酸ビニル共
重合体を少なくとも30重量部混合し、これに亜鉛
化合物の少なくとも一種類、および、アンチモ
ン、モリブテン、けい素、アルミニウム、マグネ
シウム、カルシウムそれぞれの酸化物、水酸化物
あるいは炭酸塩のうちの少なくとも一種類を添加
してなることを特徴とするポリ塩化ビニル組成
物。1. At least 30 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% or more is mixed with 100 parts by weight of polyvinyl chloride, and at least one type of zinc compound, antimony, molybdenum, A polyvinyl chloride composition comprising at least one of the oxides, hydroxides, and carbonates of silicon, aluminum, magnesium, and calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6931782A JPS58185636A (en) | 1982-04-23 | 1982-04-23 | Polyvinyl chloride composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6931782A JPS58185636A (en) | 1982-04-23 | 1982-04-23 | Polyvinyl chloride composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58185636A JPS58185636A (en) | 1983-10-29 |
| JPS6241613B2 true JPS6241613B2 (en) | 1987-09-03 |
Family
ID=13399054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6931782A Granted JPS58185636A (en) | 1982-04-23 | 1982-04-23 | Polyvinyl chloride composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58185636A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4719762B2 (en) * | 2008-03-26 | 2011-07-06 | 長島鋳物株式会社 | Fall prevention ladder for underground structures |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5245650A (en) * | 1975-10-09 | 1977-04-11 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin compositions |
| JPS5269953A (en) * | 1975-12-08 | 1977-06-10 | Uniroyal Inc | Polyvinyl halogenideeplasticizer composition |
| JPS5316751A (en) * | 1976-07-31 | 1978-02-16 | Matsushita Electric Works Ltd | Vinyl chloride resin compositions |
| JPS5359749A (en) * | 1976-10-14 | 1978-05-29 | Nl Industries Inc | Halogenncontained plastic composition having flame retardant and smoke retardant property |
| JPS5447344A (en) * | 1977-09-21 | 1979-04-13 | Kanegafuchi Chemical Ind | Gasket for fire door |
| JPS54127456A (en) * | 1978-03-13 | 1979-10-03 | Uniroyal Inc | Composition having smoking decreasing property |
| JPS5538884A (en) * | 1978-09-11 | 1980-03-18 | Nl Industries Inc | Fire and smoke retardant of halogen contained plastic composition |
| JPS55116746A (en) * | 1979-03-01 | 1980-09-08 | Nissan Chem Ind Ltd | Chlorine-containing resin composition |
| JPS5692940A (en) * | 1979-12-27 | 1981-07-28 | Sumitomo Bakelite Co Ltd | Flame-retardant thermoplastic resin composition |
-
1982
- 1982-04-23 JP JP6931782A patent/JPS58185636A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5245650A (en) * | 1975-10-09 | 1977-04-11 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin compositions |
| JPS5269953A (en) * | 1975-12-08 | 1977-06-10 | Uniroyal Inc | Polyvinyl halogenideeplasticizer composition |
| JPS5316751A (en) * | 1976-07-31 | 1978-02-16 | Matsushita Electric Works Ltd | Vinyl chloride resin compositions |
| JPS5359749A (en) * | 1976-10-14 | 1978-05-29 | Nl Industries Inc | Halogenncontained plastic composition having flame retardant and smoke retardant property |
| JPS5447344A (en) * | 1977-09-21 | 1979-04-13 | Kanegafuchi Chemical Ind | Gasket for fire door |
| JPS54127456A (en) * | 1978-03-13 | 1979-10-03 | Uniroyal Inc | Composition having smoking decreasing property |
| JPS5538884A (en) * | 1978-09-11 | 1980-03-18 | Nl Industries Inc | Fire and smoke retardant of halogen contained plastic composition |
| JPS55116746A (en) * | 1979-03-01 | 1980-09-08 | Nissan Chem Ind Ltd | Chlorine-containing resin composition |
| JPS5692940A (en) * | 1979-12-27 | 1981-07-28 | Sumitomo Bakelite Co Ltd | Flame-retardant thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58185636A (en) | 1983-10-29 |
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