JPH07278391A - Antistatic vinylic polymer composition containing chlorine and molding - Google Patents
Antistatic vinylic polymer composition containing chlorine and moldingInfo
- Publication number
- JPH07278391A JPH07278391A JP10056194A JP10056194A JPH07278391A JP H07278391 A JPH07278391 A JP H07278391A JP 10056194 A JP10056194 A JP 10056194A JP 10056194 A JP10056194 A JP 10056194A JP H07278391 A JPH07278391 A JP H07278391A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- antistatic
- polymer composition
- weight
- parts
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、帯電防止性にすぐれた
塩素含有ビニル系重合体組成物および成形物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing vinyl polymer composition having excellent antistatic properties and a molded product.
【０００２】[0002]
【従来の技術】塩素含有ビニル系重合体を帯電防止する
ためには、帯電防止剤を樹脂に配合する方法が一般に行
なわれている。 帯電防止剤としては、陽イオン系、非
イオン系、または陰イオン系の界面活性剤であり一般に
はアミド類、第４アンモニウム化合物、ポリアルキレン
グリコ−ル誘導体、サルフェ−ト類及びサルホネ−ト
類、ならびにその他のエ−テル類および水酸基含有のエ
ステル類である。 この種の帯電防止剤はそれ自体良好
な帯電防止効果を示すものであるが、塩素含有ビニル系
重合体に対する分散性及び相溶性に劣るという欠点を有
している。 又、この種の帯電防止剤を配合した塩素含
有ビニル系重合体成形品の実際上の帯電防止性は性能上
充分でなかった。 すなわち、帯電防止効果が一時的な
もので持続性がなかったり、添加した帯電防止剤などが
成形品の表面にブリ−ドして成形品を汚染し、水洗や摩
擦等により帯電防止効果が著しく低下するなどの欠点を
有する。2. Description of the Related Art A method of incorporating an antistatic agent into a resin is generally used to prevent the chlorine-containing vinyl polymer from being charged. The antistatic agent is a cationic, nonionic or anionic surfactant, and is generally an amide, a quaternary ammonium compound, a polyalkylene glycol derivative, a sulfate and a sulfoneate. , And other ethers and hydroxyl group-containing esters. Although this kind of antistatic agent exhibits a good antistatic effect by itself, it has a drawback that it is inferior in dispersibility and compatibility with a chlorine-containing vinyl polymer. In addition, the chlorine-containing vinyl polymer molded product containing this kind of antistatic agent has an insufficient antistatic property in practice. That is, the antistatic effect is temporary and not long-lasting, or the added antistatic agent bleeds on the surface of the molded product to contaminate the molded product, and the antistatic effect is remarkable by washing with water or rubbing. It has drawbacks such as deterioration.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
の従来の帯電防止剤を配合してえられる塩素含有ビニル
系重合体組成物の欠点を解決し、すぐれた帯電防止効果
があり、かつ、ブリ−ドのない帯電防止性塩素含有ビニ
ル系重合体組成物および成形物を提供することにある。The object of the present invention is to solve the drawbacks of the chlorine-containing vinyl polymer composition obtained by blending the above-mentioned conventional antistatic agent, and to have an excellent antistatic effect. Another object of the present invention is to provide an antistatic chlorine-containing vinyl polymer composition having no bleed and a molded article.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記課題を
解決するために種々検討を重ねた結果、塩素含有ビニル
系重合体１００重量部に対してオキシエチレン単位２〜
５０個を有するメタクリレ−ト重合体０．１〜１００重
量部およびアルカリ金属塩およびアルカリ土類金属塩か
ら選ばれた１種以上の化合物０．０１〜２０重量部を配
合することにより帯電防止性にすぐれた塩素含有ビニル
系重合体組成物および成形物を見出した。As a result of various studies to solve the above problems, the present inventor has found that 2 parts of oxyethylene units are added to 100 parts by weight of a vinyl polymer containing chlorine.
Antistatic property by blending 0.1 to 100 parts by weight of a methacrylate polymer having 50 and 0.01 to 20 parts by weight of one or more compounds selected from alkali metal salts and alkaline earth metal salts. The excellent chlorine-containing vinyl polymer composition and molded product were found.
【０００５】すなわち本発明は、塩素含有ビニル系重合
体１００重量部に対して、オキシエチレン単位を２〜５
０個を有するメタクリレ−ト重合体０．１〜１００重量
部およびアルカリ金属塩およびアルカリ土類金属塩から
選ばれた１種以上の化合物を０．０１〜２０重量部を配
合することを特徴とする帯電防止性にすぐれた塩素含有
ビニル系重合体組成物および成形物である。That is, in the present invention, 2 to 5 oxyethylene units are added to 100 parts by weight of a vinyl polymer containing chlorine.
0.1 to 100 parts by weight of a methacrylate polymer having 0 and 0.01 to 20 parts by weight of one or more compounds selected from alkali metal salts and alkaline earth metal salts. A chlorine-containing vinyl polymer composition and a molded article having excellent antistatic properties.
【０００６】本発明に使用されるオキシエチレン単位を
含有するメタクリレ−ト重合体としては、オリゴ（オキ
シエチレン）メタクリレ−ト重合体、メタクリレ−ト−
オリゴ（オキシエチレン）メタクリレ−ト共重合体、ポ
リ末端カルボンオリゴ（オキシエチレン）メタクリレ−
ト重合体、メチルメタクリレ−ト重合体−ｂ−オリゴ
（オキシエチレン）メタクリレ−ト重合体ブロック共重
合体などをあげることができる。The methacrylic acid polymer containing an oxyethylene unit used in the present invention includes an oligo (oxyethylene) methacrylic acid polymer and a methacrylic acid polymer.
Oligo (oxyethylene) methacrylate copolymer, poly-terminated carbo-oligo (oxyethylene) methacrylate
Examples of the polymer include a methyl polymer, a methyl methacrylate polymer-b-oligo (oxyethylene) methacrylate block copolymer, and the like.
【０００７】本発明のメタクリレ−ト重合体中のオキシ
エチレン単位の数が、２個より少ない場合にはイオン解
離能力が小さくなり、帯電防止性が付与されにくく、ま
た、５０個より多い場合には相溶が悪くなる傾向にあ
り、力学的物性が損われる。When the number of oxyethylene units in the methacrylate polymer of the present invention is less than 2, the ionic dissociation ability becomes small and the antistatic property is hardly imparted, and when the number is more than 50. Has a tendency to become poorly compatible, and its mechanical properties are impaired.
【０００８】また、その配合割合は塩素含有ビニル系重
合体１００重量部に対し、０．１〜１００重量部であ
り、好ましくは１〜５０重量部である。The blending ratio is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the chlorine-containing vinyl polymer.
【０００９】また、本発明において配合されるアルカリ
金属塩およびアルカリ土類金属塩は導電性を付与し、帯
電を防止させるための成分であり、たとえば、カチオン
部位としては、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ等が挙げら
れ、アニオン部位としては、Ｃｌ、Ｂｒ、Ｉ、ＢＦ4、
ＢＦ6、ＣＦ3ＳＯ3 、ＣｌＯ4 、ＮＯ3、ＣＯ3等が挙げ
られる。 これらの中で特に過塩素酸リチウムおよび
トリフルオロメタンスルホン酸リチウムが有効に用いら
れる。Further, the alkali metal salt and the alkaline earth metal salt blended in the present invention are components for imparting conductivity and preventing electrification. For example, as the cation site, Li, Na, K, Mg, Ca, etc. are mentioned, and as an anion site, Cl, Br, I, BF 4 ,
Examples thereof include BF 6 , CF 3 SO 3 , ClO 4 , NO 3 , and CO 3 . Of these, lithium perchlorate and lithium trifluoromethanesulfonate are particularly effectively used.
【００１０】本発明において配合されるアルカリ金属塩
およびアルカリ土類金属塩の割合は、塩素含有ビニル系
重合体１００重量部に対して、０．０１〜２０重量部
で、好ましくは、０．０５〜５重量部である。 ０．０
１重量部未満では、導電性の向上はほとんどなく、帯電
防止の効果が小さく、また、２０重量部を越えると結晶
が析出しやすくなり、重合体組成物は脆くなる傾向にあ
る。The proportion of the alkali metal salt and the alkaline earth metal salt compounded in the present invention is 0.01 to 20 parts by weight, preferably 0.05, based on 100 parts by weight of the chlorine-containing vinyl polymer. ~ 5 parts by weight. 0.0
If it is less than 1 part by weight, the conductivity is hardly improved and the antistatic effect is small, and if it exceeds 20 parts by weight, crystals tend to be precipitated and the polymer composition tends to be brittle.
【００１１】本発明における塩素含有ビニル系重合体と
は、ポリ塩化ビニル、ポリ塩化ビニリデン及びポリ塩化
ビニルもしくはポリ塩化ビニリデンと酢酸ビニルやその
他のビニル化合物との共重合体のような塩素含有化合物
を構成単位とするビニル系重合体の総称である。The chlorine-containing vinyl polymer in the present invention means a chlorine-containing compound such as polyvinyl chloride, polyvinylidene chloride and polyvinyl chloride or a copolymer of polyvinylidene chloride and vinyl acetate or other vinyl compound. It is a general term for vinyl polymers used as constituent units.
【００１２】上記の塩素含有ビニル系重合体には、本発
明に係わる配合において、用途に応じて、安定剤、充填
剤、滑剤、着色剤等の各種添加剤を適宜配合することが
できる。 特に安定剤としてはポリオ−ル部分エステル
および又はポリオ−ル、亜鉛化合物およびハイドロタル
サイトを添加した系は「亜鉛ヤケ」防止を相乗的に増大
させ、著しい熱安定性改良効果を示す。 また場合によ
って、従来知られている各種の帯電防止剤や帯電防止性
可塑剤あるいは酸化防止剤と併用することも差支えな
い。Various additives such as stabilizers, fillers, lubricants, colorants and the like can be appropriately added to the above chlorine-containing vinyl polymer in the compounding according to the present invention depending on the application. In particular, as a stabilizer, a system in which a polyol partial ester and / or a polyol, a zinc compound and hydrotalcite are added synergistically increases the prevention of "zinc burn", and exhibits a remarkable thermal stability improving effect. In some cases, it may be used in combination with various conventionally known antistatic agents, antistatic plasticizers or antioxidants.
【００１３】本発明の組成物および成形品を製造するた
めの混合方法は公知の方法で行なうことができる。The mixing method for producing the composition and molded article of the present invention can be carried out by a known method.
【００１４】[0014]
【発明の効果】優れた帯電防止効果をもち、ブリ−ドの
改善された塩素含有ビニル系重合体組成物および成形物
が得られる。EFFECTS OF THE INVENTION A chlorine-containing vinyl polymer composition and a molded article having an excellent antistatic effect and an improved bridging are obtained.
【００１５】[0015]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１６】［実施例および比較例］ ［シ−トの作成］表１に示す配合およびプレス条件でミ
キシングロ−ルで混合し、プレス成型により塩素含有ビ
ニル系重合体組成物のシ−トを作成した。[Examples and Comparative Examples] [Preparation of Sheet] A sheet of chlorine-containing vinyl polymer composition was prepared by mixing with mixin-gall under the composition and pressing conditions shown in Table 1 and press-molding. Created.
【００１７】［帯電防止効果の持続性試験］表１に示し
た条件で作製された塩素含有ビニル系重合体組成物のシ
−トを用いてＪＩＳ Ｋ６７２３に準じて体積固有抵抗
値を測定した。 さらにそのシ−トの表面を家庭用洗剤
を含ませた布で２０回拭き取りをおこないヘヤ−ドライ
ヤ−で乾燥後、再度、体積固有抵抗値を測定した結果を
表２に示す。[Persistence test of antistatic effect] Using a sheet of the chlorine-containing vinyl polymer composition prepared under the conditions shown in Table 1, the volume resistivity value was measured according to JIS K6723. Furthermore, the surface of the sheet was wiped 20 times with a cloth impregnated with household detergent, dried with a hair dryer, and the volume resistivity value was measured again.
【００１８】表１および表２において［Ａ］および
［Ｂ］は以下に示す重合体または化合物である。 ［Ａ］ オキシエチレン単位を含有するメタクリレ−ト
重合体 Ｉ ：オリゴ（オキシエチレン）メタクリレ−ト重合体 オキシエチレン単位：７ 極限粘度０．７２ｄｌ／ｇ（クロロホルム溶液２５℃） ＩＩ：メチルメタクリレ−ト重合体−ｂ−オリゴ（オキ
シエチレン）メタクリレ−ト重合体ブロック共重合体 オキシエチレン単位：２１ 極限粘度０．５５ｄｌ／ｇ（クロロホルム溶液２５℃） ［Ｂ］ アルカリ金属塩およびアルカリ土類金属塩から
えらばれた化合物 ａ：ＬｉＣｌＯ4 ｂ：ＬｉＣＦ3ＳＯ3 [A] and [B] in Tables 1 and 2 are the following polymers or compounds. [A] Methacrylate Polymer Containing Oxyethylene Unit I: Oligo (oxyethylene) Methacrylate Polymer Oxyethylene Unit: 7 Intrinsic Viscosity 0.72 dl / g (Chloroform Solution 25 ° C.) II: Methyl Methacrylate Polymer-b-oligo (oxyethylene) methacrylate block copolymer Oxyethylene unit: 21 Intrinsic viscosity 0.55 dl / g (chloroform solution 25 ° C.) [B] Alkali metal salt and alkaline earth metal salt Compound a: LiClO 4 b: LiCF 3 SO 3
【表１】 [Table 1]
【表２】 [Table 2]
Claims (4)
量部に（Ｂ）エチレンオキシド単位を２〜５０個含有す
るメタクリレ−ト重合体０．１〜１００重量部および
（Ｃ）アルカリ金属塩およびアルカリ土類金属塩から選
ばれた１種以上の化合物０．０１〜２０重量部を配合す
ることを特徴とする帯電防止性塩素含有ビニル系重合体
組成物および成形物1. 0.1 to 100 parts by weight of (A) a methacrylic acid polymer containing 2 to 50 ethylene oxide units in 100 parts by weight of a chlorine-containing vinyl polymer and (C) an alkali metal salt and Antistatic chlorine-containing vinyl polymer composition and molded article, characterized by blending 0.01 to 20 parts by weight of one or more compounds selected from alkaline earth metal salts
量部である請求項１記載の帯電防止性塩素含有ビニル系
重合体組成物および成形物2. The antistatic chlorine-containing vinyl polymer composition and molded article according to claim 1, wherein the blending amount of the component (B) is 1 to 50 parts by weight.
５重量部である請求項１記載の帯電防止性塩素含有ビニ
ル系重合体組成物および成形物3. The blending amount of the component (C) is from 0.05 to
5 parts by weight of the antistatic chlorine-containing vinyl polymer composition and molded product according to claim 1.
たはトリフルオロメタンスルホン酸リチウムを含む１種
以上の化合物である請求項１記載の帯電防止性塩素含有
ビニル系重合体組成物および成形物4. The antistatic chlorine-containing vinyl polymer composition and molded article according to claim 1, wherein the component (C) is one or more compounds containing lithium perchlorate or lithium trifluoromethanesulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056194A JPH07278391A (en) | 1994-04-13 | 1994-04-13 | Antistatic vinylic polymer composition containing chlorine and molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056194A JPH07278391A (en) | 1994-04-13 | 1994-04-13 | Antistatic vinylic polymer composition containing chlorine and molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07278391A true JPH07278391A (en) | 1995-10-24 |
Family
ID=14277343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10056194A Pending JPH07278391A (en) | 1994-04-13 | 1994-04-13 | Antistatic vinylic polymer composition containing chlorine and molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07278391A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012211303A (en) * | 2011-03-23 | 2012-11-01 | Riken Vitamin Co Ltd | Kneading-type antistatic agent and thermoplastic resin composition containing the same, and molded article |
| WO2013094262A1 (en) * | 2011-12-21 | 2013-06-27 | 理研ビタミン株式会社 | Kneading-type antistatic agent, thermoplastic resin composition including said agent, and molded article |
| JP2017057328A (en) * | 2015-09-18 | 2017-03-23 | 理研ビタミン株式会社 | Manufacturing method of milling type antistatic agent |
-
1994
- 1994-04-13 JP JP10056194A patent/JPH07278391A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012211303A (en) * | 2011-03-23 | 2012-11-01 | Riken Vitamin Co Ltd | Kneading-type antistatic agent and thermoplastic resin composition containing the same, and molded article |
| WO2013094262A1 (en) * | 2011-12-21 | 2013-06-27 | 理研ビタミン株式会社 | Kneading-type antistatic agent, thermoplastic resin composition including said agent, and molded article |
| CN104011164A (en) * | 2011-12-21 | 2014-08-27 | 理研维生素株式会社 | Kneading-type antistatic agent,thermoplastic resin composition including same and modled artcle |
| JP2017057328A (en) * | 2015-09-18 | 2017-03-23 | 理研ビタミン株式会社 | Manufacturing method of milling type antistatic agent |
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