JPS59230057A - Antistatic agent for synthetic polymer - Google Patents
Antistatic agent for synthetic polymerInfo
- Publication number
- JPS59230057A JPS59230057A JP10354983A JP10354983A JPS59230057A JP S59230057 A JPS59230057 A JP S59230057A JP 10354983 A JP10354983 A JP 10354983A JP 10354983 A JP10354983 A JP 10354983A JP S59230057 A JPS59230057 A JP S59230057A
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- Japan
- Prior art keywords
- graft polymer
- component
- parts
- comb
- antistatic agent
- 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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Abstract
Description
【発明の詳細な説明】
本発明は合成高分子材料用帯電防止剤に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic agent for synthetic polymeric materials.
一般に合成高分子材料は電気抵抗率が大きく、摩擦、は
く離によって容易に帯電しゃすく、ゴミやホコリを吸引
して外観を損ねる等成形品、シート、フィルム、繊維等
の製品分野で様々なトラブルを起こしている。Synthetic polymer materials generally have a high electrical resistivity, and they easily charge up due to friction or peeling, and they attract dirt and dust, causing various problems in the product field such as molded products, sheets, films, and fibers, such as damaging the appearance. It's happening.
従来よりこのような帯電しゃすい合成高分子材料に帯電
防止性を付与する検討がなされており、その手段を大別
すると次のように分類することができる。Conventionally, studies have been made to impart antistatic properties to such charge-resistant synthetic polymer materials, and the means for achieving this can be broadly classified as follows.
１、帯電防止剤の内部練込み法。1. Internal kneading method of antistatic agent.
２、帯電防止剤の表面塗布法。2. Surface application method of antistatic agent.
３、シリコン系化合物の表面塗布法。3. Surface coating method of silicon-based compounds.
４、合成高分子構造の化学的改質法。4. Chemical modification method of synthetic polymer structure.
このうち帯電防止剤の内部練込み法は、永久的な帯電防
止法には成功しておらず、表面に存在する帯電防止剤は
水洗、摩擦等の手段で除去され易く、その結果帯電防止
効果が失なわれる。例外的にポリエチレン、ポリプロピ
レン、ポリ塩化ビニルなどで耐洗浄性のある内部練込み
凰帯電防止剤が実用化されているが、洗浄後帯電防止効
果が回復するまで時間を必要とすること、帯電防止剤が
表面にブリードしすぎるとゴミやホコリの粘着が起こる
こと等の欠点がある。Among these methods, the method of internally kneading an antistatic agent has not been successful as a permanent antistatic method, and the antistatic agent present on the surface is easily removed by washing with water, friction, etc., resulting in an antistatic effect. is lost. Exceptionally, internally kneaded antistatic agents that are wash-resistant have been put into practical use for polyethylene, polypropylene, polyvinyl chloride, etc., but they require time to recover their antistatic effect after washing, and they are difficult to prevent static electricity. If the agent bleeds to the surface too much, there are drawbacks such as dirt and dust sticking together.
界面活性剤全表面に塗布する方法は、洗浄によって帯電
防止効果が激減する。When the surfactant is applied to the entire surface, the antistatic effect is drastically reduced by washing.
シリコン系化合物を表面に塗布する方法は、帯電防止効
果も優れ半永久的な帯電防止効果も期待できるが、塗布
工程が必要であり、作業能率も悪くコスト的に不利な面
がある。The method of applying a silicon-based compound to the surface has an excellent antistatic effect and can be expected to have a semi-permanent antistatic effect, but it requires a coating process and has poor work efficiency and is disadvantageous in terms of cost.
合成高分子構造を化学的に改質する方法は、合成高分子
に親水基を重合その他の方法で導入する方法であるが、
一般に帯電防止効果を発揮するためにはかなり多量の親
水基を含む必要があり、そのため吸湿によって機械的性
質や他の物性に影響を及はす。The method of chemically modifying the structure of synthetic polymers is to introduce hydrophilic groups into synthetic polymers by polymerization or other methods.
In general, in order to exhibit an antistatic effect, it is necessary to contain a fairly large amount of hydrophilic groups, and as a result, mechanical properties and other physical properties are affected by moisture absorption.
本発明者等は、これら従来の欠点に鑑み鋭意研究した結
果、本発明に到達したものである。The present inventors have arrived at the present invention as a result of intensive research in view of these conventional drawbacks.
即ち本発明はＳ Ｏｎ Ｍ基及び／又はポリエチレンオ
キサイド成分（以下これら全親水性成分と称する）及び
合成高分子材料と相溶性のある成分（以下アンカー成分
と称する）を有するクシ型グラフトポリマーからなる合
成高分子材料用帯電防止剤である。That is, the present invention consists of a comb-shaped graft polymer having an S On M group and/or a polyethylene oxide component (hereinafter referred to as the total hydrophilic component) and a component compatible with the synthetic polymer material (hereinafter referred to as the anchor component). Antistatic agent for synthetic polymer materials.
ただし、Ｍはアルカリ金属
本発明は、帯電防止効果及びその持続性にすぐれた帯電
防止剤として、親水性成分を幹にもち、アンカー成分を
枝とするクシ型グラフトポリマーが有用であるという事
実に基づいてなされ念ものである。However, M is an alkali metal The present invention is based on the fact that a comb-shaped graft polymer having a hydrophilic component as a trunk and an anchor component as a branch is useful as an antistatic agent with excellent antistatic effect and long-lasting effect. It is a pity that this was done based on this.
本発明に用いられるクシ型グラフトポリマーの合成法と
しては、マクロモノマー法が％に有利であり、それは従
来から知られている連鎖移動法、放射線グラフト法、ポ
リマー開始剤法等のグラフトポリマー合成法に比べ、マ
クロモノマー法によるグラフトポリマー合成法は
■枝および幹成分のホモポリマーの含有量が少ないＯ
■枝部分の分子量、グラフトポリマー全体の分子量、枝
と幹との重量比がよくコントロールできる。As a method for synthesizing the comb-shaped graft polymer used in the present invention, the macromonomer method is highly advantageous, and it is a method for synthesizing graft polymers such as the conventionally known chain transfer method, radiation grafting method, polymer initiator method, etc. Compared to this method, the graft polymer synthesis method using the macromonomer method (1) has a small content of homopolymer in the branch and trunk components; (2) has good control over the molecular weight of the branch portion, the molecular weight of the entire graft polymer, and the weight ratio of the branches and the trunk.
〇目的に応じて枝成分と幹成分の組合わせを自由に選べ
る。〇You can freely choose the combination of branch components and trunk components depending on your purpose.
等の特長があるからである。This is because it has the following features.
本発明におけるマクロモノマーとは、分子鎖の片末端に
重合性の官能基をもつ、比較的低分子量（数平均分子量
で、ｉ、ｏ ｏ ｏ〜ｉ ｏ、ｏ ｏ ｏ ）のオリゴ
マーを意味する。本発明におけるマクロモノマーの末端
重合性官能基の例としては、アクリロイルオキシ、メタ
クリロイルオキシ、アリルオキシ、スチリル等のビニル
重合タイプのものをあげることができる。In the present invention, the macromonomer refers to an oligomer with a relatively low molecular weight (in number average molecular weight, i, o o o to i o, o o o) that has a polymerizable functional group at one end of the molecular chain. . Examples of the terminal polymerizable functional group of the macromonomer in the present invention include those of vinyl polymerization type such as acryloyloxy, methacryloyloxy, allyloxy, and styryl.
また、本発明におけるマクロモノマー法とは、マクロモ
ノマーと低分子量モノマーとの共重合によるクシ型グラ
フトポリマーの製造法を意味する。Moreover, the macromonomer method in the present invention means a method for producing a comb-shaped graft polymer by copolymerizing a macromonomer and a low molecular weight monomer.
クーど型グラフトポリマーの製造におけるアン加成分と
しては、使用枠始する合成高分子材料と同一成分は勿論
、使用する合成高分子材料と相溶性のある成分を選べば
よく、そのような成分を構成するモノマーとしては例え
ばアルキルアクリレート、アルキルメタクリレート、ス
チレン等ヲあげることができる。As an additional component in the production of a Kudo-type graft polymer, it is sufficient to select not only the same component as the synthetic polymer material to be used, but also a component that is compatible with the synthetic polymer material to be used. Examples of constituent monomers include alkyl acrylate, alkyl methacrylate, and styrene.
本発明で用いるクシ型グラフトポリマーは、例えば親水
性成分を有するラジカル重合性モノマーと上記マクロモ
ノマーとのラジカル共重合により容易に合成することが
でき、幹は親水性成分、枝はマクロモノマー成分からな
るクシ型グラフトポリマーが得られる。The comb-shaped graft polymer used in the present invention can be easily synthesized, for example, by radical copolymerization of a radically polymerizable monomer having a hydrophilic component and the above-mentioned macromonomer, and the trunk is made from the hydrophilic component and the branches are made from the macromonomer component. A comb-shaped graft polymer is obtained.
一例を示せば、ポリメタクリル酸メチルを枝とするクシ
型グラ７トボリマーの合成は、メタクリル酸メチルをチ
オグリコール酸共存下にラジカル重合して分子量１，０
００〜１０，０００の片末端カルボン酸プレポリマーを
得、これをメタクリル酸グリシジルと反応させることに
よジメタクリル酸エステル渦末端基を有するマクロモノ
マーとする。このマクロモノマーに対し共重合成分とし
て親水性成分を有するラジカル重合性モノマーを使用す
れば、幹が親水性成分で枝がポリメタクリル酸メチルの
クシ型グラフトポリマーが得られる。To give an example, a comb-shaped graphite polymer having polymethyl methacrylate as a branch can be synthesized by radical polymerization of methyl methacrylate in the coexistence of thioglycolic acid with a molecular weight of 1.0.
00 to 10,000 is obtained, and this is reacted with glycidyl methacrylate to produce a macromonomer having a dimethacrylate ester vortex terminal group. If a radically polymerizable monomer having a hydrophilic component is used as a copolymerization component for this macromonomer, a comb-shaped graft polymer having a hydrophilic component as the trunk and polymethyl methacrylate as the branches can be obtained.
本発明におけるクシ型グラフトポリマー中の親水性成分
としては、Ｓｏ、Ｍ基及び／又はポリエチレンオキサイ
ド成分である。The hydrophilic components in the comb-shaped graft polymer in the present invention include So, M groups and/or polyethylene oxide components.
親水性成分がこれらの成分で構成されるとき、該クシ型
グラフトポリマーを合成高分子材料に配合すると、極め
て優れた帯電防止能を有すると共に、一般に使用されて
いる四級アンモニウム塩型帯電防止剤に比べ、耐熱性、
相溶性の優れた帯電防止剤が得られる。When the hydrophilic component is composed of these components, when the comb-shaped graft polymer is blended with a synthetic polymer material, it has an extremely excellent antistatic ability and can be used as a commonly used quaternary ammonium salt type antistatic agent. Heat resistance compared to
An antistatic agent with excellent compatibility can be obtained.
クシ型グラフトポリマーの幹に親水性成分を導入する方
法としては、前述の如く、親水性成分を有するラジカル
重合性モノマーを使用するが、該モノマーとしては、Ｓ
Ｏ，Ｍ基を有するラジカル重合性モノマー、マクロモノ
マーと共重合しクシ型グラフトポリマーとした後に、Ｓ
Ｏ，Ｍ成分を導入できるラジカル重合性モノマー（以下
Ｓｏ、Ｍ導入モノマーと称する）及びアルキレンオキサ
イド成分を有するラジカル重合性モノマー等テあす、具
体的にはＳｏ、Ｍ基を有するラジカル重合性モノ資とし
ては、Ｐ−スチレンスルホン酸アルカリ金属塩、２−ア
クリルアミド−２−メチルプロパンスルホン酸アルカリ
金属塩、アクリロイルオキシエチルスルホン酸アルカリ
金属塩、３−メタクリロイルオキシグロビルスルホン酸
アルカリ金属塩等をあげることができる。ＳＯ，Ｍ導入
モノマートシてはアクリル酸、メタクリル酸、マレイン
酸、イタコン酸、及びこれらから誘導されカルボキシル
基を有するモノマー例えば２−メタクリロイルオキシエ
チルアシッドスクシネート、２−メタクリロイルオキシ
エチルアシッド７タレート、２−メタクリロイルオキシ
エチルアシッドヘキサヒドロ７タレート等をあげること
ができるが、このうちアクリル酸、メタクリル酸が入手
の容易さ、コストの点で特に好ましい。As a method for introducing a hydrophilic component into the backbone of a comb-shaped graft polymer, a radically polymerizable monomer having a hydrophilic component is used as described above.
After copolymerizing with a radically polymerizable monomer having O and M groups and a macromonomer to form a comb-shaped graft polymer, S
Radical polymerizable monomers that can introduce O and M components (hereinafter referred to as So and M introduction monomers) and radical polymerizable monomers that have alkylene oxide components, specifically radical polymerizable monomers that have So and M groups. Examples include alkali metal salts of P-styrenesulfonic acid, alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid, alkali metal salts of acryloyloxyethylsulfonic acid, alkali metal salts of 3-methacryloyloxyglobylsulfonic acid, etc. I can do it. SO,M-introduced monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and monomers derived from these and having a carboxyl group, such as 2-methacryloyloxyethyl acid succinate, 2-methacryloyloxyethyl acid 7-talate, Examples include -methacryloyloxyethyl acid hexahydro-7-thalerate, among which acrylic acid and methacrylic acid are particularly preferred in terms of ease of availability and cost.
５０１１Ｍ導入モノマーを使用する場合の８０．Ｍ成分
導入の方法としては、上記したアクリル酸を例にとれば
、アクリル酸とマクロモノマーを共重合し、幹にカルボ
キシル基を有するクシ型グラフトポリマーを得、ＮａＯ
Ｈ等により中和することによって、カルボキシル基をソ
ーダ塩とし、引き続き、プロパンサルトル等と液塩を反
応させることにより、Ｓｏ、Ｎａ成分を導入することが
できる。80 when using 5011M introduced monomer. Taking the above-mentioned acrylic acid as an example, the method for introducing the M component is to copolymerize acrylic acid and a macromonomer to obtain a comb-shaped graft polymer having a carboxyl group in the trunk, and then
By neutralizing with H or the like, the carboxyl group is converted into a soda salt, and then by reacting the liquid salt with propane sartore or the like, So and Na components can be introduced.
スルホン酸の対イオン（Ｍ）としては、帯電防止性を発
揮させるために、アルカリ金属であることが必要であり
、具体的にはカリウム、ナトリウム、リチウムが好まし
い。The counter ion (M) of the sulfonic acid needs to be an alkali metal in order to exhibit antistatic properties, and specifically, potassium, sodium, and lithium are preferable.
また、ポリエチレンオキサイド成分を有するラジカル重
合性モノマーとしては、次式（Ｉ）、（６）に示すモノ
マーが使用できる。Further, as the radically polymerizable monomer having a polyethylene oxide component, monomers shown in the following formulas (I) and (6) can be used.
ＣＨ２＝Ｃ−Ｃ−０＋Ｃ山Ｃ迅０−）−Ｘ （Ｉ
）（鳥は水素又はメチル基、Ｘは水素又は炭素数１〜９
のデルキル基、ｍは４≦ｍ≦５００の整数）Ｘは水素又
は炭素数１〜９のアルキル基であるが、炭素数１０以上
のアルキル基を有するモノマーは、一般に製造が困難で
ある。CH2=C-C-0+C mountain C Xun 0-)-X (I
) (Bird is hydrogen or methyl group, X is hydrogen or carbon number 1-9
(m is an integer of 4≦m≦500) X is hydrogen or an alkyl group having 1 to 9 carbon atoms, but monomers having an alkyl group having 10 or more carbon atoms are generally difficult to produce.
エチレンオキサイド基は４〜５００個が好ましいが、９
〜５０個がさらに好ましい。The number of ethylene oxide groups is preferably 4 to 500, but 9
-50 pieces is more preferable.
アルキレンオキサイド基の数が４未満の場合には帯電防
止性を付与しにくく、又、５００より多い場合には重合
性が悪くなりゃすい。When the number of alkylene oxide groups is less than 4, it is difficult to impart antistatic properties, and when it is more than 500, polymerizability tends to deteriorate.
これら親水性成分を有するラジカル重合性モノマーは、
単独あるいは２種類以上を併用することができる。These radically polymerizable monomers having hydrophilic components are
They can be used alone or in combination of two or more.
本発明クシ型グラフトポリマー中における親水性成分の
割合は、該クシ型グラフトポリマー中、５〜９０重量％
が好ましく、１０〜８０重量％がさらに好ましい。親水
性成分の割合が５重量％未満の場合には、優れた帯電防
止効果を発揮するのに多量の該クシ型グラフトポリマー
の添加が必要となり、経済的に不利を招き、合成高分子
材料本来の性能を損ないやすい。又、親水性成分の割合
が９０重量％を越えると、アンカー成分の割合が少なく
なるため、帯電防止効果についての耐久性が悪くなり、
又、合成高分子材料との相溶性も悪くなりやすい。The proportion of the hydrophilic component in the comb-shaped graft polymer of the present invention is 5 to 90% by weight in the comb-shaped graft polymer.
is preferable, and 10 to 80% by weight is more preferable. If the proportion of the hydrophilic component is less than 5% by weight, it is necessary to add a large amount of the comb-shaped graft polymer to exhibit an excellent antistatic effect, resulting in an economical disadvantage and performance is likely to be impaired. Furthermore, when the proportion of the hydrophilic component exceeds 90% by weight, the proportion of the anchor component decreases, resulting in poor durability of the antistatic effect.
Furthermore, the compatibility with synthetic polymer materials tends to deteriorate.
本発明におけるクシ型グラフトポリマーの枝成分は前記
した如く、マクロモノマー成分であり、該マクロモノマ
ーは対象とする合成高分子材料と同一成分はもちろん、
相溶性のある成分であればよく、広範囲に選ぶことがで
きる。As mentioned above, the branch component of the comb-shaped graft polymer in the present invention is a macromonomer component, and the macromonomer may be the same component as the target synthetic polymer material, or
Any component can be selected from a wide range as long as it is compatible.
例えば枝成分がポリメタクリル酸メチルより成るグラフ
トポリマーはポリメタクリル酸メチルの帯電防止効果に
有効なばかりでなく、ポリメタクリル酸メチルと親和性
のあるポリ塩化ビニル、ポリエチレンテレフタレート、
エポキシ樹脂などの帯電防止にも用いることができる。For example, a graft polymer whose branch component is polymethyl methacrylate is not only effective in antistatic effect of polymethyl methacrylate, but also polyvinyl chloride, polyethylene terephthalate, which has affinity with polymethyl methacrylate, and polymethyl methacrylate.
It can also be used to prevent static electricity in epoxy resins and the like.
本発明クシ型グラフトポリマーの合成高分子材料への添
加量は０．５〜１０重量％が好ましく、１〜５重量％が
さらに好ましい。The amount of the comb-shaped graft polymer of the present invention added to the synthetic polymer material is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight.
添加量が０．５重量部未満では充分な帯電防止効果が得
られに〈＜、又、１００重量部越える添加では、合成高
分子材料本来の性能が損なわれたり、経済的に不利とな
る。If the amount added is less than 0.5 parts by weight, a sufficient antistatic effect cannot be obtained. If the amount added exceeds 100 parts by weight, the inherent performance of the synthetic polymer material may be impaired or it may be economically disadvantageous.
本発明におけるクシ型グラフトポリマーの合成高分子材
料への添加方法については、通常の帯電防止剤の使用法
、例えば帯電防止剤を適当な溶媒に溶解した溶液を、合
成高分子材料表面へ塗布、吹付、あるいは該溶液中に合
成高分子材料を浸漬することにより帯電防止剤を合成高
分子材料表面に付着させる方法、あるいは、ペレット成
形時又は製品の成形加工時に帯電防止剤を添加、混練す
る方法がそのまま採用されるが、前者の方法では、一般
に操作上複雑であり、溶媒の合成高分子材料表面への影
響が心配されるのに対し、後者の方法では、操作が簡便
である。Regarding the method of adding the comb-shaped graft polymer to the synthetic polymer material in the present invention, the usual method of using an antistatic agent is used, for example, applying a solution of the antistatic agent dissolved in a suitable solvent to the surface of the synthetic polymer material. A method in which an antistatic agent is attached to the surface of a synthetic polymer material by spraying or immersing the synthetic polymer material in the solution, or a method in which an antistatic agent is added and kneaded during pellet molding or product molding processing. The former method is generally complicated in operation and there are concerns about the influence of the solvent on the surface of the synthetic polymer material, whereas the latter method is simple in operation.
このような利点に加え、本発明で用いるクシ凰グラフト
ポリマーは前述したように帯電防止性は勿論、合成高分
子材料との相溶性、熱安定性にも優れた性質を具備し７
ているので、実用上は後者の内部練込み法を採用するの
が非常に好ましい。In addition to these advantages, the Kushio graft polymer used in the present invention has not only antistatic properties but also excellent compatibility with synthetic polymer materials and thermal stability, as described above.
Therefore, in practice, it is highly preferable to adopt the latter internal kneading method.
クシ型グラフトポリマーを添加した合成高分子材料の優
れた帯電防止効果の発現の次めには、クシ型グラフトポ
リマーが合成高分子材料表面へ移行（ｔたは濃縮という
）−する必要があるが、本発明におけるクシ型グラフト
ポリマーを配合した合成高分子材料はその製品の成形加
工時に通常適用されている合成高分子材料のガラス転移
温度以上の温度、時間、金属製金型音用いることにより
、その高分子材料表面にクシ型グラフトポリマーを容易
に移行させることができる。成形温度が合成高分子材料
のガラス転移温度未満の温度では、クシ型グラフトポリ
マーの合成高分子材料表面への移行が難しくなり、優れ
た帯電防止効果は発揮できなくなりやすい。Next to the development of the excellent antistatic effect of a synthetic polymer material to which a comb-shaped graft polymer is added, the comb-shaped graft polymer must be transferred (referred to as concentration) to the surface of the synthetic polymer material. The synthetic polymer material blended with the comb-shaped graft polymer of the present invention can be manufactured by using a temperature, time, and metal mold noise higher than the glass transition temperature of the synthetic polymer material that is normally applied during the molding process of the product. The comb-shaped graft polymer can be easily transferred to the surface of the polymer material. If the molding temperature is lower than the glass transition temperature of the synthetic polymer material, it will be difficult for the comb-shaped graft polymer to transfer to the surface of the synthetic polymer material, and the excellent antistatic effect will likely not be exhibited.
本発明における合成高分子材料としては、各種の合成高
分子材料が使用できるが、そのうちポリメタクリル酸メ
チル、ポリ塩化ビニル、ポリエチレンテレフタレート、
エポキシ樹脂、ポリスチレン等に有効に使用できる。Various synthetic polymer materials can be used as the synthetic polymer material in the present invention, among which polymethyl methacrylate, polyvinyl chloride, polyethylene terephthalate,
Can be effectively used for epoxy resin, polystyrene, etc.
本発明の合成高分子材料用帯電防止剤は、合成高分子材
料の本来の性能を損なわず、優れた帯電防止効果を発揮
し、ま念合成高分子材料表面から簡単に離脱することな
く、帯電防子効果を持続するのである。The antistatic agent for synthetic polymer materials of the present invention exhibits an excellent antistatic effect without impairing the original performance of the synthetic polymer material, and does not easily detach from the surface of the synthetic polymer material. It maintains the protective effect.
次に実施例及び比較例をあげて本発明をさらに具体的に
説明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
尚、各側において、部は重量部を表わし、係は重量％を
表わす。In addition, on each side, parts represent parts by weight, and ratios represent weight %.
また、各側において得られた試験片の帯電防止性能は、
スタチツクオネストメーターを用いて帯電圧の牛減期を
測定することにより判定した。In addition, the antistatic performance of the test pieces obtained on each side was
Judgment was made by measuring the shelf life of the electrostatic voltage using a static honest meter.
尚、スタチツクオネストメーターの測定条件は次のとお
りである。The measurement conditions of the static honest meter are as follows.
印加電圧 １０ＫＶ
印加時間 ６０秒
測定湿度 ５５％ＲＨ測定温度
２３℃
参考例１
末端メタクリレート型メチルメタクリレートマクロモノ
マーの合成
撹拌機、還流冷却器、滴下ロート、温度計及びＮガス吹
込口を備えたガラスフラスコにアセトン１７．５部、ト
ルエン８２．５部の混合溶媒を仕込み、丸導入還流下に
、メチルメタクリレート（以下ＭＭＡと略記する）１０
０部、連鎖移動剤としてチオグリコール酸（以下ＴＧＡ
と略記する）９．２部及び重合開始剤としてアゾビスイ
ソブチロニトリル（以下ＡＩＢＮと略記する）３部の混
合溶液′ｆ：３時間連続的に滴下して重合を行った。さ
らにその後２時間加熱して重合を終了した。Applied voltage: 10KV Application time: 60 seconds Measured humidity: 55% RH Measured temperature
23°C Reference Example 1 Synthesis of terminal methacrylate type methyl methacrylate macromonomer Mix 17.5 parts of acetone and 82.5 parts of toluene in a glass flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and N gas inlet. After charging the solvent, methyl methacrylate (hereinafter abbreviated as MMA) 10 was added under reflux.
0 parts, thioglycolic acid (hereinafter TGA) as a chain transfer agent
A mixed solution 'f of 9.2 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 3 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator was continuously added dropwise for 3 hours to carry out polymerization. Thereafter, the mixture was heated for 2 hours to complete the polymerization.
反応液の一部をｎ−ヘキサンにて沈澱後、減圧下で乾燥
して酸価を測定したところ１．０４０”１１／ｆであっ
た。A portion of the reaction solution was precipitated with n-hexane, dried under reduced pressure, and the acid value was measured to be 1.040''11/f.
次に上記反応液からアセトンの一部を留去した後、触媒
としてトリエチルアミン０．５１、重合防止剤としてハ
イドロキノン七ノメチルエーテル２００ ｐｐｍ及び酸
価に対し、１．２倍モルのグリシジルメタクリレートを
加え、反応温度１１０℃にて４時間反応させた。酸化の
減少から求めた反応率は９８チであった。Next, after distilling off part of the acetone from the above reaction solution, 0.51 of triethylamine as a catalyst, 200 ppm of hydroquinone hepta-methyl ether as a polymerization inhibitor, and 1.2 times the mole of glycidyl methacrylate based on the acid value were added. , the reaction was carried out at a reaction temperature of 110° C. for 4 hours. The reaction rate determined from the reduction in oxidation was 98%.
反応液を１０倍量のｎ−ヘキサン中に投入して沈澱させ
た後、８０℃で減圧乾燥を行い、下記構造式ＣＩ）のマ
クロモノマー９５部を得た。ゲルパーミェーションクロ
マドグ９７（ＧＰＣ）によるポリスチレン換算分子量は
９７０（数平均）及び２２５０（重量平均）であった。The reaction solution was poured into 10 times the volume of n-hexane for precipitation, and then dried under reduced pressure at 80°C to obtain 95 parts of a macromonomer of the following structural formula CI). The polystyrene equivalent molecular weight measured by Gel Permeation Chroma Dog 97 (GPC) was 970 (number average) and 2250 (weight average).
又、水酸基価は■−当量 １．０７０ ／ｌであった。Also, the hydroxyl value is ■-equivalent It was 1.070/l.
参考例２
クシ型グラフトポリマーの合成
参考例１と同様の装置に、参考例１で得たマクロモノマ
ー８０部、アクリル酸２０部、Ｔ Ｇ Ａ ’１部、溶
媒としてエタノール７５部、テトラヒドロ７ラン２２５
部及びＡＩＢＮａ部を仕込み、Ｎ導入６５℃で２４時間
反応させた。Reference Example 2 Synthesis of Comb-shaped Graft Polymer Into the same apparatus as in Reference Example 1, 80 parts of the macromonomer obtained in Reference Example 1, 20 parts of acrylic acid, 1 part of TGA', 75 parts of ethanol as a solvent, and 7 parts of tetrahydro were added. 225
1 part and AIBNa part were charged, and N was reacted at 65° C. for 24 hours.
この反応液を約１０倍量のｎ−へ牟サンに投入沈澱させ
、８０℃で減圧下乾燥してグラフトポリマー９８部を得
た。This reaction solution was poured into about 10 times the amount of n-hemusan for precipitation, and dried at 80° C. under reduced pressure to obtain 98 parts of a graft polymer.
ＧＰＣによるポリスチレン換算数平均分子量は約３，０
００であった。The number average molecular weight in terms of polystyrene by GPC is approximately 3.0
It was 00.
参考例３
５０ｇＮａ屋グラフドグリマーの合成
参考例２で得られｆｃＣＯＯＨ含有クシ型グラフトポリ
マー１００部をエタノール１００部、テトラヒドロ７ラ
ン３００部の混合溶媒に加温しながらビーカー内で溶か
した。次いで、１０１ＮａＯＨ−メタノール溶液で中和
を行い、約１０倍量のｎ−ヘキサンに投入沈澱し、８０
℃で減圧下乾燥を行なった。Reference Example 3 Synthesis of 50 g Na-ya Grafted Glimmer 100 parts of the fcCOOH-containing comb-shaped graft polymer obtained in Reference Example 2 was dissolved in a mixed solvent of 100 parts of ethanol and 300 parts of tetrahydro-7 in a beaker while heating. Next, it was neutralized with a 101 NaOH-methanol solution, and precipitated in about 10 times the amount of n-hexane.
Drying was performed under reduced pressure at °C.
この固体全量を撹拌機、還流冷却器、滴下ロート、温度
計を備えたフラスコに入れ、トルエン１７００部を加え
、加熱して分散させた後、還流下で滴下ロートよりプロ
パンサルトン４２部を約３０分かかり滴下反応させた。The entire amount of this solid was put into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 1,700 parts of toluene was added, and the mixture was heated and dispersed. Approximately 42 parts of propane sultone was added from the dropping funnel under reflux. The dropwise reaction took 30 minutes.
その後、さらに１時間加熱還流を行い、ガスクロマトグ
ラフィーによりプロパンサルトンのピークの減少全確認
してスルホン化反応を終え次。約１０倍量のｎ−へキサ
ンに投入沈澱し、８０℃で減圧下乾燥を行い、目的物の
Ｓ Ｏｓ Ｎ ａ Ｋｉｎグラフトポリマーを１１７１
７部得
参考例４
８０、Ｎａ及びポリエチレングリコール型グラフトポリ
マーの合成
参考例２と同様の装置に、参考例１のマクロモノマー４
０部、メトキシポリエチレングリコールモノメタクリレ
ート（分子量約１．０００ ）３０部及びアクリル酸３
０部、ＴＧＡＩ部により同様の方法にて、共重合を行っ
た。Thereafter, the mixture was further heated under reflux for 1 hour, and the sulfonation reaction was completed by confirming the decrease in the propane sultone peak by gas chromatography. The target S Os Na Kin graft polymer was precipitated in approximately 10 times the volume of n-hexane and dried under reduced pressure at 80°C.
7 parts obtained Reference Example 4 Synthesis of 80, Na and polyethylene glycol type graft polymer Macromonomer 4 of Reference Example 1 was placed in the same apparatus as Reference Example 2.
0 parts, 30 parts of methoxypolyethylene glycol monomethacrylate (molecular weight approximately 1.000), and 3 parts of acrylic acid.
Copolymerization was carried out in the same manner using 0 part and TGAI part.
その後、参考例３と同様の方法により、プロパンサルト
ン６３部使用してスルホン化反応ヲ行なった。目的物の
Ｓ Ｏ３Ｎ ａ及びポリエチレングリコール型グラフト
ポリマーを１４７４７部得参考例５
ポリエチレングリコール型グラフトポリマーの合参考例
２と同様の装置に、参考例１のマクロモノマー２０部、
ポリエチレングリコールモノメタクリレート（分子量約
４５０）８０部及びメルカプトエタノール１部により同
様の方法にて共重合を行い、目的物のポリエチレングリ
コール型グラフトポリマーｔ−６６部得た、
参考例６
Ｓ Ｏ，Ｎ ａ型グラフトポリマーの合成参考例２と同
様の装置に、参考例１のマクロモノマー３０部、ＭＭＡ
５０部、Ｐ−スチレンスルホン酸ソーダ２０部、溶媒と
してＮ、 Ｎ−ジメチルホルムアミド４００部及びＡＩ
ＢＮａ部により同様の方法により共重合を行い、溶媒を
８０℃減圧下乾燥により除去して目的物のＳ Ｏｓ Ｎ
ａ ｍグラフトポリマー９８部を得比。Thereafter, a sulfonation reaction was carried out in the same manner as in Reference Example 3 using 63 parts of propane sultone. Obtained 14,747 parts of target S O3N a and polyethylene glycol type graft polymer Reference Example 5 Synthesis of polyethylene glycol type graft polymer Into the same apparatus as in Reference Example 2, 20 parts of the macromonomer of Reference Example 1,
Copolymerization was carried out in the same manner using 80 parts of polyethylene glycol monomethacrylate (molecular weight approximately 450) and 1 part of mercaptoethanol to obtain t-66 parts of the desired polyethylene glycol type graft polymer. Reference Example 6 SO, Na Synthesis of type graft polymer Into the same apparatus as in Reference Example 2, 30 parts of the macromonomer of Reference Example 1 and MMA were added.
50 parts, 20 parts of sodium p-styrene sulfonate, 400 parts of N,N-dimethylformamide as a solvent, and AI
Copolymerization was carried out using the same method using the BNa portion, and the solvent was removed by drying at 80°C under reduced pressure to obtain the target product S Os N.
98 parts of a m graft polymer were obtained.
実施例１
ポリ塩化ビニル樹脂（東亜合成化学工業（株）裂開品名
アロンＴＳ−７００）１００部に熱安定剤としてジブチ
ルスズマレート３部を混合したボリ塩化ビニル樹脂組成
物１００部に参考例３で得られたＳｏｓＮａｍグラフト
ポリマーを３部混合し、熱二本ロールで１７０℃（ロー
ル表面温度）×５分間ブレンドした。得られたブレンド
物をプレスにて成形し、厚さ２■、５ｃｒｎ角のシーＩ
ｆ得た。Example 1 Reference Example 3 was added to 100 parts of a polyvinyl chloride resin composition prepared by mixing 100 parts of a polyvinyl chloride resin (Toagosei Kagaku Kogyo Co., Ltd., cleavage product name: Aron TS-700) with 3 parts of dibutyltin malate as a heat stabilizer. Three parts of the SosNam graft polymer obtained above were mixed and blended using two heated rolls at 170°C (roll surface temperature) for 5 minutes. The obtained blend was molded using a press to form a sheet I with a thickness of 2 cm and a square of 5 cm.
I got f.
プレス条件は２枚のクロムメッキ鋼板の間に該ブレンド
物と厚さ２ｍのスペーサーを入れ、プレス圧８０ｋｇ／
ｄｘ １８０℃×５分の熱プレスを行い、続いて直ちに
プレス圧８０ｋｌ？／ｃＩＩＩＸ２０ｔｌ：Ｘ５分の急
冷プレスの条件で行なった。得られた厚さ２■、５ｃｒ
ｎ角のシートラ試験片として、湿度５５チＲＨ，温度２
３℃の雰囲気に１日放置後、上記の方法により帯電圧半
減期を測定したところ、１３秒であった０又、該Ｓ Ｏ
ｓ Ｎ ａ型グラフトポリマーのみを配合しないポリ塩
化ビニル樹脂組成物を同様に実験したとζろ、帯電圧半
減期は１時間以上であった。The press conditions were as follows: The blend and a 2 m thick spacer were placed between two chrome-plated steel plates, and the press pressure was 80 kg/
dx Heat press at 180°C for 5 minutes, then immediately press at a pressure of 80kl? /cIIIX20tl: The test was carried out under the conditions of quenching press for 5 minutes. Obtained thickness 2cm, 5cr
As an n-square sheetra test piece, the humidity was 55 degrees RH and the temperature was 2.
After being left in an atmosphere at 3°C for one day, the half-life of the charged voltage was measured using the method described above, and it was found to be 13 seconds.
When a similar experiment was conducted using a polyvinyl chloride resin composition in which only the sN a type graft polymer was not blended, the half-life of the charging voltage was 1 hour or more.
実施例２〜４
実施例１と同じポリ塩化ビニル樹脂組成物１００部に参
考例４で得られたＳＯ，Ｎａ及びポリエチレングリコー
ル型グラフトポリマーを３部混合し、以下実施例１と同
じ操作を行ない帯電圧半減期を測定した。その結果を表
−１に実施例２として示した。又参考例５で得られたポ
リエチレングリコール型グラフトポリマーを用い同様に
操作し帯電圧半減期を測定した結果を表−１に実施例３
として、又参考例６で得られたＳＯ，Ｎａ型グラフトポ
ＩＪ？−を用い同様に操作し、帯電圧半減期を測定した
結果を表−１に実施例４として示した０
表−１
実施例５・６、比較例１
ポリメタクリル酸メチル（三菱レーヨン（株）層高品名
ＢＲ−６０）１００部と参考例３で得られたＳ Ｏ，Ｎ
ａ型グラフトポリマー３部とを１７０℃の温度でラボ
プラストミルで５分間ブレンドした。Examples 2 to 4 Three parts of the SO, Na and polyethylene glycol type graft polymer obtained in Reference Example 4 were mixed with 100 parts of the same polyvinyl chloride resin composition as in Example 1, and the same operations as in Example 1 were carried out. The half-life of the charging voltage was measured. The results are shown in Table 1 as Example 2. In addition, the polyethylene glycol type graft polymer obtained in Reference Example 5 was operated in the same manner and the charging voltage half-life was measured. Table 1 shows the results of Example 3.
Also, the SO, Na type graft topo IJ? obtained in Reference Example 6 The half-life of the charging voltage was measured using - and the results are shown in Table 1 as Example 4. Table 1 Examples 5 and 6, Comparative Example 1 Polymethyl methacrylate (Mitsubishi Rayon Co., Ltd. 100 parts of layered product name BR-60) and SO,N obtained in Reference Example 3
3 parts of a-type graft polymer were blended at a temperature of 170° C. for 5 minutes in a laboplasto mill.
得られたブレンド物をプレスにて成形し、厚さ２■、５
ｃｆＲ角のシートを得た。プレス条件は２枚のクロムメ
ッキ鋼板の間に該ブレンド物と厚さ２ｍのスペーサーを
入れ、プレス圧８０ ｋｇ／ｃｒ／１ｘ１５０と
℃×５分の、熱１、プレス＃行ない、続いて直ちにプレ
ス圧８０ｋｇ／ｃｒ／１Ｘ２０℃×５分の急冷プレスの
条件で行なった。得られた厚さ２■、５の角のシートを
試験片として、以下実施例１と同様の方法で帯電圧半減
期を測定した。その結果を表−２に実施例５として示し
た０又参考例４で得られたＳ Ｏ８Ｎ ａ及びポリエチ
レングリコール型グラ７ドボリマーを用い同様に操作し
、帯電圧半減期を測定した結果を表−２に実施例６とし
て示した。The obtained blend was molded using a press to give thicknesses of 2 cm and 5 cm.
A sheet with a cfR angle was obtained. The pressing conditions were to place the blend and a 2 m thick spacer between two chrome-plated steel plates, press pressure 80 kg/cr/1x150, heat 1, press # for 5 minutes at ℃, and then press immediately. The test was carried out under the conditions of quench pressing at a pressure of 80 kg/cr/1×20° C.×5 minutes. The half-life of the charged voltage was measured in the same manner as in Example 1 using the resulting sheet with a thickness of 2 cm and 5 squares as a test piece. The results are shown in Table 2 as Example 5. The same operation was carried out using the SO8N a obtained in Reference Example 4 and the polyethylene glycol type grade polymer, and the half-life of the charged voltage was measured. The results are shown in Table 2. 2 as Example 6.
一方、これらグラフトポリマーを配合しない同じポリメ
タクリル酸メチルを同様に操作し、帯電圧半減期を測定
した結果を表−２に比較例１として示した。On the other hand, the same polymethyl methacrylate without these graft polymers was operated in the same manner, and the half-life of the charging voltage was measured. The results are shown in Table 2 as Comparative Example 1.
表−２
特許出願人
東亜合成化学工業株式会社
手続補正書
昭和５８年７月２５日
特許庁長官 若 杉 和 夫 殿
１、事件の表示
昭和５８年特許願第１０３５４９号
２、発明の名称
合成高分子材料用帯電防止剤
３、補正をする者
事件との関係 特許出願人
住所 東京都港区西新横１丁目１４番１号４、補正の
対象
明細書の発明の詳細な説明の欄
５、補正の内容
（１）明細書箱１５頁３行目に「酸化」とあるを、１１
１ｉ１１＋ｊ 、！ｌ［スル。Table 2 Patent Applicant Toagosei Kagaku Kogyo Co., Ltd. Procedural Amendment July 25, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of Case 1983 Patent Application No. 103549 2, Name of Invention Synthetic High Antistatic Agent for Molecular Materials 3, Relationship with the case of the person making the amendment Patent applicant address: 1-14-1-4 Nishishinyoko, Minato-ku, Tokyo, Column 5 of the detailed description of the invention in the specification to be amended, Amendment Contents (1) The word "oxidation" on page 15, line 3 of the specification box has been changed to 11
1i11+j,! l [Suru.
Claims (1)
成分′及び合成高分子材料と相溶性のある成分を有する
クシ型グラフトポリマーからなる合成高分子材料用帯電
防止剤。 ただし、Ｍはアルカリ金属[Claims] 1. An antistatic agent for synthetic polymeric materials comprising a comb-shaped graft polymer having a SosM group and/or a polyethylene oxide component' and a component compatible with the synthetic polymeric material. However, M is an alkali metal
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10354983A JPS59230057A (en) | 1983-06-11 | 1983-06-11 | Antistatic agent for synthetic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10354983A JPS59230057A (en) | 1983-06-11 | 1983-06-11 | Antistatic agent for synthetic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59230057A true JPS59230057A (en) | 1984-12-24 |
| JPH0238110B2 JPH0238110B2 (en) | 1990-08-29 |
Family
ID=14356901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10354983A Granted JPS59230057A (en) | 1983-06-11 | 1983-06-11 | Antistatic agent for synthetic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59230057A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02242843A (en) * | 1989-03-15 | 1990-09-27 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| WO1999045055A1 (en) * | 1998-03-07 | 1999-09-10 | Beiersdorf Ag | Sulfonated comb polymers and preparations, especially hair cosmetic preparations based on such sulfonated comb polymers |
| EP1052267A3 (en) * | 1999-05-14 | 2000-11-22 | Beiersdorf Aktiengesellschaft | Combination of water soluble and/or water dispersible, silicon modified, comb polymers and one or more substances chosen from the group of physiologically acceptable anionic or amphoteric polymers |
| EP1043352A3 (en) * | 1999-04-07 | 2000-11-22 | Beiersdorf Aktiengesellschaft | Silicon modified, sulfonated comb polymers and preparations, especially hair cosmetic preparations based on such silicon modified sulfonated comb polymers |
| EP1048287A3 (en) * | 1999-04-30 | 2000-11-22 | Beiersdorf AG | Mixtures of water soluble and/or water dispersible, silicon modified, comb polymers and one or more substances chosen from the group of physiologically acceptable anionic or amphoteric polymers |
| EP1081172A1 (en) * | 1999-09-04 | 2001-03-07 | Beiersdorf AG | Sulfonated comb polymers and preparations with selected Lithium/Sodium-ratio, especially hair cosmetic preparations based on such sulfonated comb polymers |
| WO2002018475A1 (en) * | 2000-08-31 | 2002-03-07 | Beiersdorf Ag | Silicon-modified, sulphonated comb polymers and preparations, especially hair care preparations based on said silicon-modified, sulphonated comb polymers |
| EP1082955A3 (en) * | 1999-09-08 | 2003-11-05 | Beiersdorf Aktiengesellschaft | Cosmetic and dermatological compositions containing sulfonated comb polymers |
-
1983
- 1983-06-11 JP JP10354983A patent/JPS59230057A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02242843A (en) * | 1989-03-15 | 1990-09-27 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| WO1999045055A1 (en) * | 1998-03-07 | 1999-09-10 | Beiersdorf Ag | Sulfonated comb polymers and preparations, especially hair cosmetic preparations based on such sulfonated comb polymers |
| EP1043352A3 (en) * | 1999-04-07 | 2000-11-22 | Beiersdorf Aktiengesellschaft | Silicon modified, sulfonated comb polymers and preparations, especially hair cosmetic preparations based on such silicon modified sulfonated comb polymers |
| EP1048287A3 (en) * | 1999-04-30 | 2000-11-22 | Beiersdorf AG | Mixtures of water soluble and/or water dispersible, silicon modified, comb polymers and one or more substances chosen from the group of physiologically acceptable anionic or amphoteric polymers |
| EP1052267A3 (en) * | 1999-05-14 | 2000-11-22 | Beiersdorf Aktiengesellschaft | Combination of water soluble and/or water dispersible, silicon modified, comb polymers and one or more substances chosen from the group of physiologically acceptable anionic or amphoteric polymers |
| EP1081172A1 (en) * | 1999-09-04 | 2001-03-07 | Beiersdorf AG | Sulfonated comb polymers and preparations with selected Lithium/Sodium-ratio, especially hair cosmetic preparations based on such sulfonated comb polymers |
| WO2001018091A1 (en) * | 1999-09-04 | 2001-03-15 | Beiersdorf Ag | Sulfonated comb polymers with selected lithium/sodium ratio and preparations, especially, hair-cosmetic preparations, on the basis of such sulfonated comb polymers |
| US7129299B2 (en) | 1999-09-04 | 2006-10-31 | Beiersdorf Ag | Sulphonated comb polymers having a selected lithium/sodium ratio and preparations including such polymers |
| EP1082955A3 (en) * | 1999-09-08 | 2003-11-05 | Beiersdorf Aktiengesellschaft | Cosmetic and dermatological compositions containing sulfonated comb polymers |
| WO2002018475A1 (en) * | 2000-08-31 | 2002-03-07 | Beiersdorf Ag | Silicon-modified, sulphonated comb polymers and preparations, especially hair care preparations based on said silicon-modified, sulphonated comb polymers |
| US6951913B2 (en) | 2000-08-31 | 2005-10-04 | Beiersdörf AG | Silicone-modified sulphonated comb polymers and preparations, in particular hair cosmetic preparations, based on such silicone-modified sulphonated comb polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0238110B2 (en) | 1990-08-29 |
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