JPH0570650A - Vinyl chloride based resin composition - Google Patents
Vinyl chloride based resin compositionInfo
- Publication number
- JPH0570650A JPH0570650A JP30860491A JP30860491A JPH0570650A JP H0570650 A JPH0570650 A JP H0570650A JP 30860491 A JP30860491 A JP 30860491A JP 30860491 A JP30860491 A JP 30860491A JP H0570650 A JPH0570650 A JP H0570650A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- vinyl chloride
- fatty acid
- zinc
- electrical conductivity
- 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
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【産業上の利用分野】本発明は、塩化ビニル系樹脂組成
物に関し、さらに詳しくは電気絶縁性に優れる塩化ビニ
ル系樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition having excellent electrical insulation.
【従来の技術及び発明が解決しようとする課題】塩化ビ
ニル系樹脂は、成型加工時の熱安定性や加工性、及び製
品の電気的、機械的特性を満たすため種々の安定剤や添
加剤を必要とする。その中でも電線や絶縁テープといっ
た塩化ビニル系製品においては、特に電気絶縁性と熱安
定性を必要としており、そのため三塩基性硫酸鉛やステ
アリン酸鉛といった鉛系安定剤が主として用いられてい
る。ところが近年、人体に対する安全性や産業廃棄物等
の問題から、プラスチック添加剤においてはその無毒化
がさけばれており、鉛系安定剤にかわり得る電気絶縁性
及び熱安定性を有する無毒性安定剤の開発が望まれてい
た。そこで本発明者らは、(1)ハイドロタルサイト類
化合物と、(2)3価以上の多価アルコール系化合物の
少なくとも一種及び、(3)導電率が50μ1/Ω/c
m以下の脂肪酸亜鉛を使用することにより、かかる諸問
題を解決しうることを見い出し、先に特許出願を行った
が、なるほど黒色系やグレー系の製品においてはこれら
(1)(2)(3)の組成物で何ら問題はないが、白色
系や淡色系においては着色性が不十分であるということ
が判ってきた。BACKGROUND OF THE INVENTION Vinyl chloride resins contain various stabilizers and additives in order to satisfy the thermal stability and processability during molding and the electrical and mechanical properties of products. I need. Among them, vinyl chloride products such as electric wires and insulating tapes require electrical insulation and thermal stability, and therefore lead-based stabilizers such as tribasic lead sulfate and lead stearate are mainly used. However, in recent years, due to problems such as safety for human body and industrial waste, detoxification of plastic additives has been avoided, and non-toxic stabilizers having electric insulation and thermal stability that can replace lead stabilizers. Was desired to be developed. Therefore, the present inventors have found that (1) a hydrotalcite compound, (2) at least one of trivalent or higher polyhydric alcohol compounds, and (3) a conductivity of 50 μ1 / Ω / c.
It was found that such problems can be solved by using a fatty acid zinc of m or less, and a patent application was previously filed. However, in the case of black and gray products, these (1) (2) (3 Although there is no problem with the composition of 1), it has been found that the coloring property is insufficient in the white type and the light type.
【問題を解決するための手段】本発明者らは、かかる状
況に鑑み鋭意検討の結果、ハイドロタルサイト類化合物
と、導電率が50μ1/Ω/cm以下の脂肪酸亜鉛と、
β−ジケトン化合物又はその金属塩を含有することによ
りはじめて、電気絶縁性、熱安定性及び着色性のいずれ
も優れた効果が得られることを見出したのである。すな
わち本発明は、塩化ビニル系樹脂に(1)ハイドロタル
サイト類化合物と、(2)3価以上の多価アルコール系
化合物の少なくとも一種と、(3)導電率が50μ1/
Ω/cm以下の脂肪酸亜鉛と、(4)β−ジケトン化合
物又はその金属塩を含有することを特徴とする塩化ビニ
ル系樹脂組成物である。本発明の塩化ビニル系樹脂と
は、塩化ビニル単独重合体または塩化ビニルを主体とし
た樹脂であって例えば、塩化ビニルと酢酸ビニル、塩化
ビニリデン、エチレン、プロピレン、メタアクリル酸エ
ステル、ウレタン樹脂との共重合体やグラフト重合体あ
るいはこれら樹脂とのブレンド物等である。本発明で用
いられるハイドロタルサイト類化合物としては、 で表される化合物であり、具体例としては、 Mg6Al2(OH)16CO3・4H2O Mg4.5Al2(OH)13CO3・3.5H2O Mg4.5Al2(OH)13CO3 Mg3.5Zn1.0Al2(OH)13CO3・3.
5H2O などが挙げられ、市販品では、アルカマイザー1、アル
カマイザー2、アルカマイザー3、アルカマイザー4、
アルカマイザー5、DHT−4A(いずれも協和化学工
業社製)などがある。これらのハイドロタルサイト類化
合物は塩化ビニル系樹脂100重量部に対して、0.1
〜10重量部用いられ、さらに好ましくは0.5〜5.
0重量部使用される。次に本発明で用いられる脂肪酸亜
鉛としては、例えばステアリン酸亜鉛、パルミチン酸亜
鉛、ミリスチン酸亜鉛、ラウリン酸亜鉛、オクチル酸亜
鉛、ベヘニン酸亜鉛等が挙げられ、特に導電率が50μ
1/Ω/cm以下の脂肪酸亜鉛としては、前述の各脂肪
酸と亜鉛の酸化物、水酸化物、炭酸化物との直接溶融反
応により得られるものが好適である。通常の脂肪酸をカ
セイソーダ等でケン化し、更に塩化亜鉛あるいは硫酸亜
鉛を反応させるいわゆる複分解反応で得られる脂肪酸亜
鉛を、極めて長時間水洗しても、所望の導電率50μ1
/Ω/cm以下のものは得られるが効率的ではない。こ
れらの脂肪酸亜鉛は塩化ビニル系樹脂100重量部に対
し、0.05〜5重量部用いられ、更に好ましくは、
0.1〜2.0重量部使用される。また本発明で用いら
れる3価以上の多価アルコール化合物としては種々のも
のが制限なく使用でき、例えば、ジトリメチロールエタ
ン、トリメチロールプロパン、グリセリン、マンニトー
ル、ソルビトール、ペンタエリスリトール、ジペンタエ
リスリトール、ジペンタエリスリトール・アジピン酸部
分エステルなどが挙げられるこれらの3価以上の多価ア
ルコール化合物は、塩化ビニル系樹脂100重量部に対
し、0.05〜5重量部用いられ、更に好ましくは、
0.1〜2.0重量部使用される。次に本発明で用いら
れるβ−ジケトン化合物又はその金属塩としては、例え
ば、ジベンゾイルメタン、ステアロイルベンゾイルメタ
ン、パルミトイルベンゾイルメタン、ベンゾイルアセト
ン、ジベンゾイルメタン亜鉛、ステアロイルベンゾイル
メタン亜鉛などが挙げられる。これらの化合物は塩化ビ
ニル系樹脂100重量部に対して、0.005〜1.0
重量部用いられ、さらに好ましくは0.01〜0.5重
量部使用される。また本発明において、従来より塩化ビ
ニル系樹脂に使用されている可塑剤、充填剤、熱安定化
助剤、酸化防止剤、紫外線吸収剤、エポキシ化合物、滑
剤、顔料等を併用して良いのは言うまでもない。The present inventors have made such a situation.
As a result of diligent study in consideration of the situation, hydrotalcite compounds
And fatty acid zinc having an electric conductivity of 50 μ1 / Ω / cm or less,
By containing a β-diketone compound or a metal salt thereof,
The electrical insulation, thermal stability and colorability.
Also found that excellent effects can be obtained. sand
That is, the present invention is based on vinyl chloride resin (1) hydrotal
Site compounds and (2) trihydric or higher polyhydric alcohol
At least one of the compounds, and (3) conductivity 50μ1 /
Fatty acid zinc of Ω / cm or less and (4) β-diketone compound
Chloride containing a product or a metal salt thereof
Resin composition. With the vinyl chloride resin of the present invention
Is mainly composed of vinyl chloride homopolymer or vinyl chloride
Resins such as vinyl chloride and vinyl acetate, chloride
Vinylidene, ethylene, propylene, methacrylic acid
A copolymer or graft polymer with a stell or urethane resin.
Rui is a blend with these resins. For use in the present invention
Hydrotalcite compounds that can be used includeThe compound represented by6AlTwo(OH)16COThree・ 4HTwoO Mg4.5AlTwo(OH)ThirteenCOThree・ 3.5HTwoO Mg4.5AlTwo(OH)ThirteenCOThree Mg3.5Zn1.0AlTwo(OH)ThirteenCOThree・ 3.
5HTwoO and the like. Commercially available products include Alcamizer 1, Al
Camizer 2, Alcamizer 3, Alcamizer 4,
Alkamizer 5, DHT-4A (both Kyowa Chemical
Manufactured by a company). Assortment of these hydrotalcites
The compound is 0.1 per 100 parts by weight of vinyl chloride resin.
-10 to 10 parts by weight, more preferably 0.5 to 5.
Used 0 parts by weight. Next, the fatty acid
Examples of lead include zinc stearate and palmitic acid
Lead, zinc myristate, zinc laurate, octyl phosphite
Lead, zinc behenate, etc. are mentioned, and especially the conductivity is 50μ.
Fatty acid zinc of 1 / Ω / cm or less includes the above-mentioned fats.
Direct melting reaction of acid with zinc oxide, hydroxide and carbonate
Those obtained according to the above are suitable. Normal fatty acids
Saponification with sodium hydroxide, zinc chloride or sulfite
Fatty acids obtained by so-called metathesis reaction in which lead is reacted
Even if lead is washed with water for an extremely long time, the desired conductivity of 50μ1
A material having a resistance of less than / Ω / cm can be obtained but is not efficient. This
These fatty acid zinc are added to 100 parts by weight of vinyl chloride resin.
0.05 to 5 parts by weight, more preferably,
0.1 to 2.0 parts by weight are used. Also used in the present invention
There are various polyhydric alcohol compounds with 3 or more valences.
Can be used without limitation, for example, ditrimethylol ethanol
, Trimethylolpropane, glycerin, mannito
Le, sorbitol, pentaerythritol, dipentae
Lithritol, dipentaerythritol, adipic acid part
These trivalent or higher polyvalent monomers such as ester
The rucor compound is based on 100 parts by weight of vinyl chloride resin.
0.05 to 5 parts by weight, more preferably,
0.1 to 2.0 parts by weight are used. Then used in the present invention
Examples of the β-diketone compound or metal salt thereof include
For example, dibenzoyl methane, stearoyl benzoyl meta
, Palmitoyl benzoyl methane, benzoyl aceto
Zinc, dibenzoylmethane zinc, stearoylbenzoyl
Examples include methane zinc. These compounds are vinyl chloride
0.005-1.0 with respect to 100 parts by weight of the nil resin
It is used in parts by weight, more preferably 0.01 to 0.5 parts by weight.
Used in parts. Moreover, in the present invention, vinyl chloride has been conventionally used.
Plasticizers, fillers and heat stabilizers used for Nyl resin
Auxiliary agent, antioxidant, UV absorber, epoxy compound, lubricant
It goes without saying that agents, pigments and the like may be used in combination.
【実施例】以下実施例により具体的に説明する。 合成例1 ステアリン酸100gを130℃で溶融し、攪拌しなが
ら酸化亜鉛15.0gを少量ずつ添加した。酸化亜鉛添
加終了後30分間、攪拌熟成したのち冷却後粉砕した。
得られたステアリン酸亜鉛は導電率30μ1/Ω/c
m、融点122℃、Zn含有率10.5%であった。他
の脂肪酸についても同様に反応したものを使用した。 合成例2 ステアリン酸127.3gを90℃の温水2000cc
中に懸濁させ、カセイソーダ水溶液(413.8g/
l)44.9mlを添加した。液温を70℃に下げた
後、塩化亜鉛の水溶液(268.4g/l)を117.
5ml添加し、30分間攪拌熟成を行った。そののち反
応液をろ過し、得られたケーキを2000ccの水で2
回水洗したのち105℃の乾燥機で20時間乾燥し、粉
砕した。得られた複分解法ステアリン酸亜鉛は導電率1
80μ1/Ω/cm、融点123℃、Zn含有率10.
4%であった。なお、導電率の測定は次のように行っ
た。試料4gをコニカルビーカーに秤りとり、エチルア
ルコール5mlを加えよく混和したのちイオン交換水1
00mlを入れ、攪拌しながら30分間加熱沸騰させ
る。放冷後、ろ過し、ろ液にイオン交換水をたして10
0mlにしたのち、この液を東亜エレクトロニクス社製
のCONDUCT−METER(MODEL CM−2
A)にて測定した。 実施例1 表1の配合物を160℃の混練ロールにて5分間混練し
たのち、得られたフィルムを重ね合わせて170℃のプ
レス機で10分間プレスし、厚さ1mmのプレスシート
を作成した。得られたプレスシートを用いて、JIS
K−6723のテスト方法に準じ、体積抵抗率(30℃
で測定)及び熱安定性(180℃で測定)の評価を行
い、着色性については目視にて判定した。なお、着色性
の評価は次の通りである。 ◎:極めて優れる ○:優れる △:やや劣る ×:劣る 実施例2 表2の配合物を実施例1と同様に評価した。 Embodiments will be specifically described below with reference to embodiments. Synthesis Example 1 100 g of stearic acid was melted at 130 ° C., and 15.0 g of zinc oxide was added little by little while stirring. After the addition of zinc oxide was completed, the mixture was stirred and aged for 30 minutes, cooled, and then ground.
The obtained zinc stearate has a conductivity of 30 μ1 / Ω / c
m, melting point 122 ° C., Zn content 10.5%. For other fatty acids, those reacted in the same manner were used. Synthetic Example 2 127.3 g of stearic acid was added to warm water of 90 ° C. 2000 cc
Suspended in an aqueous solution of caustic soda (413.8 g /
l) 44.9 ml was added. After lowering the liquid temperature to 70 ° C., an aqueous solution of zinc chloride (268.4 g / l) was added to 117.
5 ml was added and aged for 30 minutes with stirring. After that, the reaction solution was filtered, and the obtained cake was washed with 2000 cc of water.
After being washed with water twice, it was dried in a drier at 105 ° C. for 20 hours and pulverized. The obtained metathesis zinc stearate has an electric conductivity of 1
80 μ1 / Ω / cm, melting point 123 ° C., Zn content 10.
It was 4%. The conductivity was measured as follows. Weigh 4 g of sample into a conical beaker, add 5 ml of ethyl alcohol and mix well, then deionize water 1
Add 00 ml and heat and boil for 30 minutes with stirring. After allowing to cool, it is filtered, and the filtrate is filled with ion-exchanged water 10
After making up to 0 ml, this liquid was used as a CONDUCT-METER (MODEL CM-2 manufactured by Toa Electronics Co., Ltd.
It was measured in A). Example 1 The formulations shown in Table 1 were kneaded with a kneading roll at 160 ° C. for 5 minutes, and the obtained films were stacked and pressed with a pressing machine at 170 ° C. for 10 minutes to prepare a press sheet having a thickness of 1 mm. .. Using the obtained press sheet, JIS
According to the test method of K-6723, volume resistivity (30 ℃
And the thermal stability (measured at 180 ° C.) were evaluated, and the colorability was visually evaluated. The evaluation of colorability is as follows. ⊚: Very good ◯: Excellent Δ: Slightly inferior ×: Inferior Example 2 The formulations in Table 2 were evaluated in the same manner as in Example 1.
【発明の効果】以上本発明に係る塩化ビニル系樹脂組成
物は、電気絶縁性(体積抵抗率)、熱安定性、着色性と
もに優れており、又、従来一般的に使用されている脂肪
酸亜鉛に比べて、導電率が50μ1/Ω/cm以下の脂
肪酸亜鉛及び3価以上の多価アルコール化合物の少なく
とも一種、そしてβ−ジケトン化合物もしくはその金属
塩を使用することにより著しく電気絶縁性(体積抵抗
率)、耐熱性、初期着色性が改善されていることが判
る。又、Mg、Al系ハイドロタルサイト(商品名:ア
ルカマイザー1)よりも、Mg・Zn・Al系ハイドロ
タルサイト(商品名:アルカマイザー4)の方が電気絶
縁性及び熱安定性に優れている。As described above, the vinyl chloride resin composition according to the present invention is excellent in electrical insulation (volume resistivity), thermal stability, and colorability, and fatty acid zinc that has been commonly used in the past. In comparison with, the use of at least one kind of fatty acid zinc having a conductivity of 50 μ1 / Ω / cm or less and a polyhydric alcohol compound having a valence of 3 or more, and a β-diketone compound or a metal salt thereof has a significantly high electrical insulation property (volume resistance). Rate), heat resistance, and initial colorability are improved. In addition, Mg / Zn / Al-based hydrotalcite (product name: Alkamizer 4) is superior to Mg and Al-based hydrotalcite (product name: Alkamizer 1) in electrical insulation and thermal stability. There is.
フロントページの続き (72)発明者 保井 宏之 大阪府堺市戎島町5丁1番地 堺化学工業 株式会社堺工場内Front page continuation (72) Inventor Hiroyuki Yasui 5-1-1 Ebishima-cho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd. Sakai Plant
Claims (1)
(2)3価以上の多価アルコール系化合物の少なくとも
一種と、(3)導電率が50μ1/Ω/cm以下の脂肪
酸亜鉛と、(4)β−ジケトン化合物又はその金属塩を
含有することを特徴とする塩化ビニル系樹脂組成物。1. A (1) hydrotalcite compound,
(2) containing at least one polyhydric alcohol compound having a valence of 3 or more, (3) fatty acid zinc having an electric conductivity of 50 μ1 / Ω / cm or less, and (4) a β-diketone compound or a metal salt thereof. A characteristic vinyl chloride resin composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30860491A JPH0570650A (en) | 1991-09-11 | 1991-09-11 | Vinyl chloride based resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30860491A JPH0570650A (en) | 1991-09-11 | 1991-09-11 | Vinyl chloride based resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0570650A true JPH0570650A (en) | 1993-03-23 |
Family
ID=17983041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30860491A Pending JPH0570650A (en) | 1991-09-11 | 1991-09-11 | Vinyl chloride based resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0570650A (en) |
-
1991
- 1991-09-11 JP JP30860491A patent/JPH0570650A/en active Pending
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