JP2003238945A - Antistatic agent and multilayer film and sheet having antistatic property - Google Patents
Antistatic agent and multilayer film and sheet having antistatic propertyInfo
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- JP2003238945A JP2003238945A JP2002082059A JP2002082059A JP2003238945A JP 2003238945 A JP2003238945 A JP 2003238945A JP 2002082059 A JP2002082059 A JP 2002082059A JP 2002082059 A JP2002082059 A JP 2002082059A JP 2003238945 A JP2003238945 A JP 2003238945A
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- polyolefin
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- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は優れた帯電防止剤及
びそれを含有する帯電防止効果とその持続性に優れた多
層ポリオレフィン系合成樹脂フィルム及びシートに関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an excellent antistatic agent and a multi-layer polyolefin synthetic resin film and sheet containing the same and having excellent antistatic effect and durability.
【０００２】[0002]
【従来の技術】一般に、ポリオレフィン系合成樹脂はそ
の優れた特性のため成型品やフィルム等様々な用途で使
用されている。しかしながら、ポリオレフィン系合成樹
脂製品はその疎水性ゆえに非常に静電気を帯びやすく、
そのため製品にゴミや埃が付着して外観をそこねたり、
加工中に電気的障害が現れたり、電子機器に用いられた
場合は誤動作を引き起こすといった大きな欠点を有して
いる。2. Description of the Related Art Generally, polyolefin synthetic resins are used in various applications such as molded products and films due to their excellent properties. However, polyolefin synthetic resin products are very liable to be charged with static electricity due to their hydrophobicity.
As a result, dust or dirt may stick to the product and damage its appearance,
It has a big defect that an electrical obstacle appears during processing, and it causes a malfunction when used in an electronic device.
【０００３】従来、これら欠点を解決する手段としてア
ニオン、カチオン、ノニオン等種々の界面活性剤を添加
する方法があり実用に供されている。しかしながらこの
界面活性剤を添加する方法は、製品成形後の短期間にお
ける帯電防止性には優れるが、製品表面にブリードアウ
トした界面活性剤が摩擦、水洗等によって失われてしま
うために長期に渡って性能を持続することが困難であ
る。更にポリオレフィン系合成樹脂製品は成形時の温度
が高温であるため界面活性剤が一部熱分解を引き起こし
成型時に発煙するとか、製品が着色したりする等の問題
がある。またポリオレフィン系合成樹脂の多層フィルム
及びシートにおいては、帯電防止性能を発揮させるため
に、表面層だけでなく内層にも帯電防止剤を添加する必
要があるため、添加量が多くなり経済的に不利な面があ
る。Conventionally, a method of adding various surfactants such as anions, cations and nonions has been put into practical use as a means for solving these drawbacks. However, this method of adding a surfactant is excellent in antistatic property in a short period after the product is molded, but the surfactant bleeding out on the product surface is lost due to friction, washing with water, etc. It is difficult to maintain performance. Furthermore, since the temperature of the synthetic polyolefin resin product is high during molding, there is a problem that the surfactant causes partial thermal decomposition to cause smoke during molding, and the product is colored. In addition, in multilayer films and sheets of polyolefin-based synthetic resin, it is necessary to add an antistatic agent not only to the surface layer but also to the inner layer in order to exert antistatic performance, so the addition amount increases and it is economically disadvantageous. There are various aspects.
【０００４】近年、これら界面活性剤使用による欠点や
問題点を解決する手段として、特開平６−８０７４２、
特開平１１−１７０４５６には、ポリエーテルエステル
アミドを主成分とし第３成分として酸変性ポリオレフィ
ン等を配合する高分子型帯電防止剤が提案されている
が、これらは性能的に満足できるものではない。また、
特開平９−３１２７３には、持続性が良好な防曇剤とし
て酸変性ポリオレフィンとモノオール型アルキレンオキ
サイド付加物とのエステル化合物が提案されている。In recent years, as means for solving the drawbacks and problems caused by the use of these surfactants, JP-A-6-80742,
Japanese Patent Application Laid-Open No. 11-170456 proposes a polymer type antistatic agent containing a polyether ester amide as a main component and an acid-modified polyolefin as a third component, but these are not satisfactory in performance. . Also,
JP-A-9-31273 proposes an ester compound of an acid-modified polyolefin and a monool type alkylene oxide adduct as an antifogging agent having good durability.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前記の界面
活性剤を添加する方法や提案されている方法の欠点を解
決しようとするものであり、優れた帯電防止剤及びそれ
を含有する帯電防止効果とその持続性に優れた多層ポリ
オレフィン系合成樹脂フィルム及びシートを提供するこ
とが課題である。DISCLOSURE OF THE INVENTION The present invention is intended to solve the drawbacks of the above-mentioned method of adding a surfactant and the proposed method, and provides an excellent antistatic agent and an antistatic agent containing the same. It is an object to provide a multilayer polyolefin-based synthetic resin film and sheet which are excellent in prevention effect and durability.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意研究した結果、特徴的な構造を有す
る酸変性ポリオレフィンのエステル化合物をポリオレフ
ィン系合成樹脂のフィルム及びシートの表面層に添加す
ることにより、帯電防止効果とその持続性に優れたポリ
オレフィン系合成樹脂のフィルム及びシートが得られる
ことを見出し、本発明に到達したものである。即ち本発
明は、両末端に水酸基を有する下記一般式（１）で表さ
れるジオール型ポリオキシアルキレン化合物Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that an ester compound of an acid-modified polyolefin having a characteristic structure is used as a surface layer of a film or sheet of a polyolefin-based synthetic resin. The present invention has been completed, and it was found that a polyolefin synthetic resin film and sheet excellent in antistatic effect and its durability can be obtained by adding to the present invention. That is, the present invention provides a diol type polyoxyalkylene compound represented by the following general formula (1) having hydroxyl groups at both ends.
【化３】
（但し、Ｘは炭素数２〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の部分の分子量が６００〜１０，０００
の範囲）と鹸化価１０〜１００（ｍｇＫＯＨ／ｇ）、分
子量が１，０００〜２０，０００の範囲の酸変性ポリオ
レフィンとのエステル化合物（Ａ）と、下記一般式
（２）で表されるモノオール型ポリオキシアルキレン化
合物[Chemical 3] (However, X represents a hydrocarbon group having 2 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the molecular weight of the polyoxyalkylene group part is 600 to 10,000.
No. 1), a saponification value of 10 to 100 (mgKOH / g), and an acid-modified polyolefin having a molecular weight of 1,000 to 20,000 (A), and a mono-compound represented by the following general formula (2). All-type polyoxyalkylene compound
【化４】
（但し、Ｒは炭素数１〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の分子量が０〜５，０００の範囲）と前
記酸変性ポリオレフィンとのエステル化合物（Ｂ）と
を、（Ａ）：（Ｂ）＝１００：０〜１０：９０（重量
比）の割合で配合した組成物であって、さらに下記数式
（１）[Chemical 4] (However, R represents a hydrocarbon group having 1 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the polyoxyalkylene group has a molecular weight in the range of 0 to 5,000) and the acid-modified polyolefin. A composition in which an ester compound (B) and (A) :( B) = 100: 0 to 10:90 (weight ratio) are mixed, and the following numerical formula (1)
【０００７】[0007]
【数１】 [Equation 1]
【０００８】（但し、ａはエステル化合物（Ａ）を得る
ための酸変性ポリオレフィンの反応量（重量）を表し、
且つｂはエステル化合物（Ａ）を得るためのジオール型
ポリオキシアルキレン化合物の反応量（重量）、ｃはエ
ステル化合物（Ａ）の配合割合（重量％）、ｄはエステ
ル化合物（Ａ）を得るためのジオール型ポリオキシアル
キレン化合物中のポリオキシアルキレン基の重量、ｅは
エステル化合物（Ｂ）を得るための酸変性ポリオレフィ
ンの反応量（重量）、ｆはエステル化合物（Ｂ）を得る
ためのモノオール型ポリオキシアルキレン化合物の反応
量（重量）、ｇはエステル化合物（Ｂ）の配合割合（重
量％）、ｈはエステル化合物（Ｂ）を得るためのモノオ
ール型ポリオキシアルキレン化合物中のポリオキシアル
キレン基の重量）で表される該組成物中のポリオキシア
ルキレン基の重量割合を表すＷが２０〜６０（重量％）
の範囲の条件を満たす組成物からなる帯電防止剤と、そ
れを多層ポリオレフィン系合成樹脂フィルム及びシート
の表面層に３〜２０重量％添加することを特徴とする帯
電防止効果とその持続性に優れた多層ポリオレフィン系
合成樹脂フィルム及びシートを提供するものである。以
下本発明を詳細に説明する。(However, a represents the reaction amount (weight) of the acid-modified polyolefin for obtaining the ester compound (A),
In addition, b is the reaction amount (weight) of the diol-type polyoxyalkylene compound for obtaining the ester compound (A), c is the blending ratio (% by weight) of the ester compound (A), and d is for obtaining the ester compound (A). The weight of the polyoxyalkylene group in the diol-type polyoxyalkylene compound, e is the reaction amount (weight) of the acid-modified polyolefin for obtaining the ester compound (B), and f is the monool for obtaining the ester compound (B). -Type polyoxyalkylene compound in the reaction amount (weight), g is the compounding ratio (weight%) of the ester compound (B), and h is the polyoxyalkylene in the monool-type polyoxyalkylene compound for obtaining the ester compound (B). W is 20 to 60 (% by weight), which represents the weight ratio of the polyoxyalkylene group in the composition represented by the weight of the group).
And an antistatic agent comprising a composition satisfying the conditions of the above range, and 3 to 20% by weight of the antistatic agent added to the surface layer of a multilayer polyolefin-based synthetic resin film and sheet, and is excellent in its durability The present invention also provides a multilayer polyolefin synthetic resin film and sheet. The present invention will be described in detail below.
【０００９】本発明に係わる化合物（Ａ）および化合物
（Ｂ）を得るための酸変性ポリオレフィンとしては、不
飽和カルボン酸、例えばアクリル酸、メタクリル酸、
（無水）マレイン酸、フマル酸等で変性した酸変性ポリ
オレフィンが挙げられ、（無水）マレイン酸を使用して
変性した酸変性ポリオレフィンを使用することが効果の
点で最も好ましい。また酸変性ポリオレフィンとして、
エチレン−アクリル酸共重合体、エチレン−メタクリル
酸共重合体、エチレン−（無水）マレイン酸共重合体、
エチレン−フマル酸共重合体、プロピレン−アクリル酸
共重合体、プロピレン−メタクリル酸共重合体、プロピ
レン−（無水）マレイン酸共重合体、プロピレン−フマ
ル酸共重合体等も挙げられ、エチレン−（無水）マレイ
ン酸共重合体、プロピレン−（無水）マレイン酸共重合
体を使用することが効果の点で好ましい。また、本発明
の酸変性ポリオレフィンの鹸化価は１０〜１００（ｍｇ
ＫＯＨ／ｇ）、分子量は１，０００〜２０，０００の範
囲であり、鹸化価が本発明の範囲外の酸変性ポリオレフ
ィンを使用した場合は、所望の帯電防止効果が得られな
い。また、分子量が１，０００より小さい酸変性ポリオ
レフィンを使用した場合は、得られた本発明のエステル
化合物とポリオレフィン樹脂との相溶性が悪く、効果が
得られない。分子量が２０，０００より大きい酸変性ポ
リオレフィンを使用した場合も同様にポリオレフィン樹
脂との相溶性が悪く、効果が得られない。Acid-modified polyolefins for obtaining the compounds (A) and (B) according to the present invention include unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
Examples thereof include acid-modified polyolefins modified with (anhydrous) maleic acid, fumaric acid and the like, and use of acid-modified polyolefins modified with (anhydrous) maleic acid is most preferable in terms of effects. As an acid-modified polyolefin,
Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene- (anhydrous) maleic acid copolymer,
An ethylene-fumaric acid copolymer, a propylene-acrylic acid copolymer, a propylene-methacrylic acid copolymer, a propylene- (anhydrous) maleic acid copolymer, a propylene-fumaric acid copolymer and the like can also be mentioned, and ethylene- ( It is preferable to use (anhydrous) maleic acid copolymer or propylene- (anhydrous) maleic acid copolymer in terms of effects. The saponification value of the acid-modified polyolefin of the present invention is 10 to 100 (mg
KOH / g), the molecular weight is in the range of 1,000 to 20,000, and the desired antistatic effect cannot be obtained when an acid-modified polyolefin having a saponification value outside the range of the present invention is used. When an acid-modified polyolefin having a molecular weight of less than 1,000 is used, the compatibility of the obtained ester compound of the present invention with the polyolefin resin is poor and the effect cannot be obtained. Similarly, when an acid-modified polyolefin having a molecular weight of more than 20,000 is used, the compatibility with the polyolefin resin is poor and the effect cannot be obtained.
【００１０】本発明に係わる前記の化合物（Ａ）を得る
ための、両末端に水酸基を有する下記一般式（１）で表
されるジオール型ポリオキシアルキレン化合物A diol type polyoxyalkylene compound represented by the following general formula (1) having a hydroxyl group at both terminals for obtaining the compound (A) according to the present invention:
【化５】
（但し、Ｘは炭素数２〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の部分の分子量が６００〜１０，０００
の範囲）としては、ポリエチレングリコール、ポリプロ
ピレングリコール、エチレンオキシドとプロピレンオキ
シドのブロックもしくはランダム共重合付加物や、炭素
数２〜１８の炭化水素基を有するジオール化合物のエチ
レンオキシド付加物、プロピレンオキシド付加物、エチ
レンオキシドとプロピレンオキシドのブロック若しくは
ランダム共重合付加物が例示できる。炭素数２〜１８の
炭化水素基としてはエチレン基、プロピレン基、ヘキサ
メチレン基、デカメチレン基等のアルキレン基が例示で
き、またオクチルフェニレン基、ノニルフェニレン基、
ドデシルフェニレン基等のアルキルフェニレン基、また
ビスフェノールＡ残基若しくは水添ビスフェノールＡ残
基等の芳香族炭化水素基等が例示でき、特に炭素数２〜
１２のアルキレン基、ビスフェノールＡ残基若しくは水
添ビスフェノールＡ残基であることが、効果の点で好ま
しい結果を与える。更に、ポリオキシアルキレン化合物
のポリオキシアルキレン基部分の分子量は、６００〜１
０，０００の範囲であるが、１，０００〜８，０００の
範囲が効果の面で好結果を与える。ポリオキシアルキレ
ン基部分の分子量が、６００より小さい場合は帯電防止
性能が不足するし、１０，０００より大きい場合はこれ
を使用して得られた本発明のエステル化合物と樹脂との
相溶性が悪く、所望の効果が発揮されない。なお、一般
式（１）で表される化合物は上記に挙げた２種以上を混
ぜ合わせて使用しても何ら支障はない。[Chemical 5] (However, X represents a hydrocarbon group having 2 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the molecular weight of the polyoxyalkylene group part is 600 to 10,000.
Range), polyethylene glycol, polypropylene glycol, a block or random copolymerization adduct of ethylene oxide and propylene oxide, an ethylene oxide adduct of a diol compound having a hydrocarbon group of 2 to 18 carbon atoms, a propylene oxide adduct, an ethylene oxide. And a block or random copolymerization adduct of propylene oxide. Examples of the hydrocarbon group having 2 to 18 carbon atoms include alkylene groups such as ethylene group, propylene group, hexamethylene group, decamethylene group, octylphenylene group, nonylphenylene group,
Examples thereof include alkylphenylene groups such as dodecylphenylene group, and aromatic hydrocarbon groups such as bisphenol A residue or hydrogenated bisphenol A residue.
A alkylene group of 12, a bisphenol A residue or a hydrogenated bisphenol A residue gives favorable results in terms of effects. Furthermore, the molecular weight of the polyoxyalkylene group portion of the polyoxyalkylene compound is 600 to 1
The range is 10,000, but the range of 1,000 to 8,000 gives good results in terms of effect. When the molecular weight of the polyoxyalkylene group portion is less than 600, the antistatic performance is insufficient, and when it is more than 10,000, the compatibility of the ester compound of the present invention obtained by using this with the resin is poor. However, the desired effect is not exhibited. The compound represented by the general formula (1) may be used as a mixture of two or more kinds mentioned above without any problem.
【００１１】本発明に係わる前記の化合物（Ｂ）を得る
ための下記一般式（２）で表されるモノオール型ポリオ
キシアルキレン化合物A monool type polyoxyalkylene compound represented by the following general formula (2) for obtaining the compound (B) according to the present invention:
【化６】
（但し、Ｒは炭素数１〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の分子量が０〜５０００の範囲）におい
て、Ｒは炭素数１〜１８の炭化水素基であり、メチル
基、エチル基、イソプロピル基、ｎ−オクチル基、２−
エチルヘキシル基、ドデシル基、オクタデシル基、オク
タデセニル基等のアルキル基やアルケニル基が例示で
き、またオクチルフェニル基、ノニルフェニル基、ドデ
シルフェニル基等のアルキルフェニル基、またモノスチ
リルフェニル基、ジスチリルフェニル基、トリスチリル
フェニル基等の芳香族炭化水素基等が例示でき、特に炭
素数１〜１２のアルキル基であることが、効果の点で好
ましい結果を与える。上記一般式（２）におけるポリオ
キシアルキレン基はポリエチレン基、ポリプロピレン
基、エチレンオキシドとプロピレンオキシドのブロック
若しくはランダム共重合基が例示でき、分子量は０〜
５，０００が良く、好ましくは１，０００〜４，０００
である。５，０００より大きい場合は樹脂との相溶性が
悪くなり所望の効果を発揮できない。なお、一般式
（２）で表される化合物は上記に挙げた２種以上を混ぜ
合わせて使用しても何ら支障はない。[Chemical 6] (However, R represents a hydrocarbon group having 1 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the molecular weight of the polyoxyalkylene group is in the range of 0 to 5000). A hydrocarbon group of methyl group, ethyl group, isopropyl group, n-octyl group, 2-
Examples thereof include alkyl groups and alkenyl groups such as ethylhexyl group, dodecyl group, octadecyl group and octadecenyl group, and alkylphenyl groups such as octylphenyl group, nonylphenyl group and dodecylphenyl group, monostyrylphenyl group and distyrylphenyl group. And aromatic hydrocarbon groups such as tristyrylphenyl group and the like, and particularly, an alkyl group having 1 to 12 carbon atoms gives preferable results in terms of effects. Examples of the polyoxyalkylene group in the above general formula (2) include a polyethylene group, a polypropylene group, a block or random copolymerization group of ethylene oxide and propylene oxide, and a molecular weight of 0 to
5,000 is good, preferably 1,000 to 4,000
Is. If it is more than 5,000, the compatibility with the resin deteriorates and the desired effect cannot be exhibited. It should be noted that the compound represented by the general formula (2) may be used as a mixture of two or more kinds mentioned above without any problem.
【００１２】本発明に係わる組成物である、前記ジオー
ル型ポリオキシアルキレン化合物と鹸化価１０〜１００
（ｍｇＫＯＨ／ｇ）、分子量１，０００〜２０，０００
の範囲の酸変性ポリオレフィンとのエステル化合物
（Ａ）と、モノオール型ポリオキシアルキレン化合物と
前記の酸変性ポリオレフィンとのエステル化合物（Ｂ）
を配合した組成物は、その配合割合が（Ａ）：（Ｂ）＝
１００：０〜１０：９０（重量比）の範囲の配合割合が
必須であるが、好ましくは８０：２０〜２０：８０の範
囲の配合割合が良い。本発明のエステル化合物（Ａ）の
配合割合が１０（重量比）より少ない場合は樹脂との相
溶性が悪くなり、本発明の主旨とするところの効果が得
られない。The diol-type polyoxyalkylene compound, which is a composition according to the present invention, and a saponification value of 10 to 100.
(MgKOH / g), molecular weight 1,000 to 20,000
Ester compound (A) with an acid-modified polyolefin in the range of 1, and an ester compound (B) with a monool-type polyoxyalkylene compound and the above acid-modified polyolefin
The composition of the composition has a composition ratio of (A) :( B) =
A blending ratio in the range of 100: 0 to 10:90 (weight ratio) is essential, but a blending ratio in the range of 80:20 to 20:80 is preferable. When the compounding ratio of the ester compound (A) of the present invention is less than 10 (weight ratio), the compatibility with the resin is deteriorated, and the effect intended by the present invention cannot be obtained.
【００１３】更に、本発明のエステル化合物（Ａ）とエ
ステル化合物（Ｂ）とを配合した組成物は、前記数式
（１）で表される該組成物中のポリオキシアルキレン基
の重量割合を表すＷ（重量％）が２０〜６０の範囲の条
件を満たすことが必須である。Ｗが２０以下の場合は帯
電防止性能が不足するし、６０以上の場合は樹脂との相
溶性が悪くなり、本発明の主旨とするところの効果が得
られない。Further, the composition of the present invention in which the ester compound (A) and the ester compound (B) are mixed represents the weight ratio of the polyoxyalkylene group in the composition represented by the above formula (1). It is essential that W (% by weight) satisfies the condition of 20 to 60. When W is 20 or less, the antistatic performance is insufficient, and when it is 60 or more, the compatibility with the resin is poor, and the effect of the gist of the present invention cannot be obtained.
【００１４】本発明に係わる組成物は、前記一般式
（１）で表されるジオール型ポリオキシアルキレン化合
物と前記酸変性ポリオレフィンとを無触媒下、１５０℃
〜３００℃で公知の方法で加熱反応し得たエステル化合
物（Ａ）と、前記一般式（２）で表されるモノオール型
ポリオキシアルキレン化合物と酸変性ポリオレフィンと
を無触媒下、１５０℃〜３００℃で公知の方法で加熱反
応し得たエステル化合物（Ｂ）とを加熱下、混合するこ
とにより容易に得ることができる。The composition according to the present invention comprises a diol type polyoxyalkylene compound represented by the general formula (1) and the acid-modified polyolefin in the absence of a catalyst at 150 ° C.
To 300 ° C at a known temperature, the ester compound (A), the monool-type polyoxyalkylene compound represented by the general formula (2), and the acid-modified polyolefin may be reacted at 150 ° C to 150 ° C without catalyst. It can be easily obtained by mixing the ester compound (B) obtained by heating reaction at 300 ° C. by a known method under heating.
【００１５】また、本発明に係わる組成物は、多層ポリ
オレフィン系合成樹脂フィルムおよびシートの表面層に
表面層合計重量の３〜２０重量％添加するが、５〜１５
重量％添加することが好ましい。３重量％より少ない場
合は帯電防止性能が不足し、２０重量％より多い添加は
効果の点では問題ないが経済的に不利である。The composition according to the present invention is added to the surface layer of the multilayer polyolefin-based synthetic resin film and sheet in an amount of 3 to 20% by weight based on the total weight of the surface layers.
Addition by weight% is preferable. If it is less than 3% by weight, the antistatic performance is insufficient, and if it is more than 20% by weight, there is no problem in terms of effect but it is economically disadvantageous.
【００１６】また、本発明に係わる多層ポリオレフィン
系合成樹脂フィルムおよびシートの表面層は、全体厚に
対して両表面合計で５〜５０％の厚さが良い。厚さが５
％より少ない場合は帯電防止性能が不足し、５０％より
多い場合は効果の点では問題ないが表面層が多い分、帯
電防止剤が増えるため経済的に不利である。The surface layer of the multilayer polyolefin-based synthetic resin film and sheet according to the present invention preferably has a total thickness of 5 to 50% with respect to the total thickness. Thickness is 5
When it is less than 50%, the antistatic performance is insufficient, and when it is more than 50%, there is no problem in terms of the effect, but the amount of the antistatic agent increases as the number of surface layers increases, which is economically disadvantageous.
【００１７】本発明に係わるポリオレフィン系合成樹脂
としては、低密度ポリエチレン、高密度ポリエチレン、
直鎖状低密度ポリエチレン、メタロセン直鎖状低密度ポ
リエチレン、ポリプロピレン、ポリブテン、エチレンと
他のα−オレフィン一種以上との共重合体、プロピレン
と他のα−オレフィン一種以上との共重合体等を挙げる
ことができる。他のα−オレフィンとしては例えばエチ
レン、ポリプロピレン、１−ブテン、４−メチル−１−
ペンテン、１−ペンテン、１−オクテン、１−デセン、
１−ドデセンが挙げられる。The polyolefin-based synthetic resin according to the present invention includes low density polyethylene, high density polyethylene,
Linear low-density polyethylene, metallocene linear low-density polyethylene, polypropylene, polybutene, copolymers of ethylene and one or more other α-olefins, copolymers of propylene and one or more other α-olefins, etc. Can be mentioned. Other α-olefins include, for example, ethylene, polypropylene, 1-butene, 4-methyl-1-
Penten, 1-pentene, 1-octene, 1-decene,
1-dodecene is mentioned.
【００１８】本発明の実施において、必要に応じ酸化防
止剤、紫外線吸収剤、アンチブロッキング剤、スリップ
剤、顔料等を配合しても何ら本発明の妨げにならない。In the practice of the present invention, the addition of an antioxidant, an ultraviolet absorber, an antiblocking agent, a slip agent, a pigment, etc., if necessary, does not hinder the present invention.
【００１９】かくして得られた本発明に係わる組成物か
らなる帯電防止剤は、多層ポリオレフィン系合成樹脂フ
ィルムおよびシートに優れた帯電防止性を与えることが
できる。即ち本発明の主旨とするところは、前記本発明
に係わる特定のエステル化合物（Ａ）と前記特定のエス
テル化合物（Ｂ）とを特定の割合で配合して、多層ポリ
オレフィン系合成樹脂フィルムおよびシートに使用する
ことであり、本発明の根幹をなすものである。本発明に
使用される組成物が、優れた帯電防止性を付与できる理
由は理論的に解明できていないが、酸変性ポリオレフィ
ンとジオール型ポリオキシアルキレン化合物との架橋反
応により生成した高分子量化されたエステル化合物
（Ａ）と、エステル化合物（Ｂ）が複雑に作用し合って
効果を発揮しているものと推察している。次に本発明を
実施例により詳細に説明するが、本発明はその趣旨を越
えない限り以下の実施例に限定されるものではない。The thus-obtained antistatic agent comprising the composition according to the present invention can impart excellent antistatic properties to multilayer polyolefin synthetic resin films and sheets. That is, the gist of the present invention is to mix the specific ester compound (A) and the specific ester compound (B) according to the present invention in a specific ratio to obtain a multilayer polyolefin-based synthetic resin film and sheet. It is used, and forms the basis of the present invention. The reason why the composition used in the present invention can impart excellent antistatic properties has not been theoretically elucidated, but it has a high molecular weight produced by a cross-linking reaction between an acid-modified polyolefin and a diol-type polyoxyalkylene compound. It is presumed that the ester compound (A) and the ester compound (B) act intricately and exert their effects. Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
【００２０】[0020]
【実施例】＜本発明の組成物の合成例＞
１．本発明の組成物１の作製
温度調節器、窒素導入管、撹拌装置（ダブルヘリカリ
翼）を備え付けた５００ｍｌフラスコに無水マレイン酸
変性ポリプロピレン（Ｍｎ３１００、鹸化価９８．１）
２７８．３部、ポリエチレングリコール（Ｍｗ１００
０）１２１．７部を仕込み、乾燥窒素ガス導入下、２２
０℃で５時間加熱攪拌することによりエステル化合物
（Ａ−１）を得た。次に、温度調節器、窒素導入管、撹
拌装置（ダブルヘリカリ翼）を備え付けた５００ｍｌフ
ラスコに無水マレイン酸変性ポリプロピレン（Ｍｎ３１
００、鹸化価９８．１）２１３．４部、メトキシポリエ
チレンポリプロピレングリコール（Ｍｗ１０００ エチ
レンオキサイド／プロピレンオキサイド（重量比）＝２
／３）１８６．６部を仕込み、同様な加熱反応を行うこ
とによりエステル化合物（Ｂ−１）を得た。上記で得た
エステル化合物（Ａ−１）と（Ｂ−１）とを重量比で８
０：２０の割合で混合することによって、本発明に係わ
る組成物１を得た。尚、本組成物の前記数式（１）にお
けるＷの値は３２．９である。EXAMPLES <Synthesis example of composition of the present invention> Preparation of composition 1 of the present invention A maleic anhydride-modified polypropylene (Mn 3100, saponification value 98.1) was placed in a 500 ml flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
278.3 parts, polyethylene glycol (Mw100
0) 121.7 parts were charged, and under the introduction of dry nitrogen gas, 22
The ester compound (A-1) was obtained by heating and stirring at 0 degreeC for 5 hours. Next, a maleic anhydride-modified polypropylene (Mn31) was placed in a 500 ml flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
00, saponification number 98.1) 213.4 parts, methoxypolyethylene polypropylene glycol (Mw 1000 ethylene oxide / propylene oxide (weight ratio) = 2
/ 3) 186.6 parts were charged and the same heating reaction was carried out to obtain an ester compound (B-1). The weight ratio of the ester compounds (A-1) and (B-1) obtained above was 8
Composition 1 according to the invention was obtained by mixing in a ratio of 0:20. The value of W in the above formula (1) of the composition is 32.9.
【００２１】２．本発明の組成物２〜１０及び比較組成
物１〜３の作製
前記本発明の組成物１の作製に準じ、表１、２、３に記
載した本発明に係わる組成物２〜１０及び比較組成物１
〜３を作製した2. Preparation of Compositions 2 to 10 of the present invention and Comparative Compositions 1 to 3 According to the preparation of the composition 1 of the present invention, Compositions 2 to 10 and Comparative Compositions according to the present invention shown in Tables 1, 2 and 3 were prepared. Thing 1
~ 3 made
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【表３】 [Table 3]
【００２５】実施例１〜実施例１６
市販のポリプロピレン樹脂を用いて共押し出し温度２３
０℃で、２４μｍを内層（コア層）とし、表３中の組成
物１〜１０を添加した３μｍの両表面層（スキン層）か
ら構成される３層フィルムを作製した。このように作製
して得られた３層フィルムを（１）２３℃、５０％ＲＨ
の条件下で２４時間放置後、帯電防止性能を測定すると
ともに（２）６０℃の温水に３０分間浸したのち、２３
℃、５０％ＲＨの条件下で２４時間放置後、帯電防止性
能を測定し実施例１〜１６を得た。結果を表４に示し
た。Examples 1 to 16 Using a commercially available polypropylene resin, the coextrusion temperature was 23.
At 0 ° C., a three-layer film having 24 μm as an inner layer (core layer) and 3 μm of both surface layers (skin layers) to which the compositions 1 to 10 in Table 3 were added was prepared. The three-layer film thus obtained is (1) 23 ° C., 50% RH
After leaving it for 24 hours under the condition of (2), measure the antistatic performance and (2) soak it in warm water of 60 ° C for 30 minutes, and then 23
After standing for 24 hours at 50 ° C. and 50% RH, the antistatic performance was measured and Examples 1 to 16 were obtained. The results are shown in Table 4.
【００２６】比較例１〜比較例５
本発明外の比較組成物の作製を表３の如く行い、次いで
実施例と同様な方法で比較組成物１〜３を添加した場
合、グリセリンモノステアレートを添加した場合および
無添加の場合の帯電防止性能を測定し、比較例１〜５を
得た。Comparative Examples 1 to 5 Comparative compositions other than the present invention were prepared as shown in Table 3, and when Comparative compositions 1 to 3 were added in the same manner as in Examples, glycerin monostearate was added. The antistatic performance with and without addition was measured, and Comparative Examples 1 to 5 were obtained.
【００２７】[0027]
【表４】 [Table 4]
【００２８】＜帯電防止性の評価＞２３℃、５０％ＲＨ
の条件下で、川口電機製作所製の超絶縁計を使用し表面
固有抵抗を測定した。<Evaluation of antistatic property> 23 ° C., 50% RH
Under the conditions, the surface resistivity was measured using a super insulation meter manufactured by Kawaguchi Denki Seisakusho.
【００２９】[0029]
【発明の効果】第４表に示す如く、本発明の組成物１〜
１０からなる帯電防止剤を多層ポリオレフィン系フィル
ムおよびシートの表面層に添加することにより、優れた
帯電防止効果とその持続性を付与することが出来る。As shown in Table 4, the composition of the present invention 1
By adding the antistatic agent consisting of 10 to the surface layer of the multilayer polyolefin film and sheet, an excellent antistatic effect and its durability can be imparted.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 101/02 Ｃ０８Ｌ 101/02 Ｆターム(参考） 4F100 AH02A AH02C AK03A AK03B AK03C AK07 AK54 AK54A AK54C AK62A AK62B AK62C AK66A AK66B AK66C AL05A AL05C AL06A AL06C AL07A AL07C BA02 BA03 BA04 BA05 BA06 BA10A BA10C BA16 CA22A CA22C EH20 JG03 JL06 YY00A YY00C 4J002 BB20W BB20X GT00 4J031 AA12 AA53 AB01 AC03 AD01 AF30 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme coat (reference) C08L 101/02 C08L 101/02 F term (reference) 4F100 AH02A AH02C AK03A AK03B AK03C AK07 AK54 AK54A AK54C AK62A AK62B AK62C AK62C AK62C AK62C AK66B AK66C AL05A AL05C AL06A AL06C AL07A AL07C BA02 BA03 BA04 BA05 BA06 BA10A BA10C BA16 CA22A CA22C EH20 JG03 JL06 YY00A YY00C 4J002 BB20W BB20X GT00 4J031 AA12 AA53 AB01 AC03 AD01 AF01
Claims (2)
（１）で表されるジオール型ポリオキシアルキレン化合
物 【化１】 （但し、Ｘは炭素数２〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の部分の分子量が６００〜１０，０００
の範囲）と鹸化価１０〜１００（ｍｇＫＯＨ／ｇ）、分
子量が１，０００〜２０，０００の範囲の酸変性ポリオ
レフィンとのエステル化合物（Ａ）と、下記一般式
（２）で表されるモノオール型ポリオキシアルキレン化
合物 【化２】 （但し、Ｒは炭素数１〜１８の炭化水素基、Ｍはエチレ
ン基および／またはプロピレン基を表し、且つポリオキ
シアルキレン基の分子量が０〜５，０００の範囲）と前
記酸変性ポリオレフィンとのエステル化合物（Ｂ）と
を、（Ａ）：（Ｂ）＝１００：０〜１０：９０（重量
比）の割合で配合した組成物であって、さらに該組成物
中のポリオキシアルキレン基の重量割合が２０〜６０重
量％の範囲である組成物からなる帯電防止剤。1. A diol type polyoxyalkylene compound represented by the following general formula (1) having a hydroxyl group at both ends: (However, X represents a hydrocarbon group having 2 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the molecular weight of the polyoxyalkylene group part is 600 to 10,000.
No. 1), a saponification value of 10 to 100 (mgKOH / g), and an acid-modified polyolefin having a molecular weight of 1,000 to 20,000 (A), and a mono-compound represented by the following general formula (2). All-type polyoxyalkylene compound (However, R represents a hydrocarbon group having 1 to 18 carbon atoms, M represents an ethylene group and / or a propylene group, and the polyoxyalkylene group has a molecular weight in the range of 0 to 5,000) and the acid-modified polyolefin. A composition comprising an ester compound (B) and (A) :( B) = 100: 0 to 10:90 (weight ratio), wherein the weight of the polyoxyalkylene group in the composition is further included. An antistatic agent comprising a composition having a ratio in the range of 20 to 60% by weight.
及びシートの全体厚に対して両表面合計で５〜５０％の
厚さを有する表面層に、請求項１に記載の帯電防止剤を
表面層重量の３〜２０重量％添加することを特徴とす
る、帯電防止効果とその持続性に優れた多層ポリオレフ
ィン系合成樹脂フィルム及びシート。2. An antistatic agent according to claim 1 is added to a surface layer having a total thickness of 5 to 50% with respect to the total thickness of the multilayer polyolefin-based synthetic resin film and sheet. A multi-layer polyolefin-based synthetic resin film and sheet excellent in antistatic effect and durability, characterized by being added in an amount of 3 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002082059A JP2003238945A (en) | 2002-02-18 | 2002-02-18 | Antistatic agent and multilayer film and sheet having antistatic property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002082059A JP2003238945A (en) | 2002-02-18 | 2002-02-18 | Antistatic agent and multilayer film and sheet having antistatic property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003238945A true JP2003238945A (en) | 2003-08-27 |
Family
ID=27785376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002082059A Pending JP2003238945A (en) | 2002-02-18 | 2002-02-18 | Antistatic agent and multilayer film and sheet having antistatic property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003238945A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006131838A (en) * | 2004-11-09 | 2006-05-25 | Takashi Sawaguchi | Multi-block copolymer |
| JP2006188678A (en) * | 2004-12-09 | 2006-07-20 | Toho Chem Ind Co Ltd | Antistatic agent and multilayer film, sheet and molding having antistaticity |
| WO2011083850A1 (en) * | 2010-01-08 | 2011-07-14 | 東邦化学工業株式会社 | Antistatic agent and resin composition containing same |
-
2002
- 2002-02-18 JP JP2002082059A patent/JP2003238945A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006131838A (en) * | 2004-11-09 | 2006-05-25 | Takashi Sawaguchi | Multi-block copolymer |
| JP4568584B2 (en) * | 2004-11-09 | 2010-10-27 | 孝志 澤口 | Multiblock copolymer |
| JP2006188678A (en) * | 2004-12-09 | 2006-07-20 | Toho Chem Ind Co Ltd | Antistatic agent and multilayer film, sheet and molding having antistaticity |
| WO2011083850A1 (en) * | 2010-01-08 | 2011-07-14 | 東邦化学工業株式会社 | Antistatic agent and resin composition containing same |
| JP2011231325A (en) * | 2010-01-08 | 2011-11-17 | Toho Chem Ind Co Ltd | Antistatic agent and resin composition containing the same |
| JP4858865B2 (en) * | 2010-01-08 | 2012-01-18 | 東邦化学工業株式会社 | Antistatic agent and resin composition containing the same |
| CN102791821A (en) * | 2010-01-08 | 2012-11-21 | 东邦化学工业株式会社 | Antistatic agent and resin composition containing same |
| US8742017B2 (en) | 2010-01-08 | 2014-06-03 | Toho Chemical Industry Co., Ltd. | Antistatic agent and resin composition containing same |
| CN102791821B (en) * | 2010-01-08 | 2015-03-25 | 东邦化学工业株式会社 | Antistatic agent and resin composition containing same |
| KR101793757B1 (en) * | 2010-01-08 | 2017-11-03 | 도호 가가꾸 고오교 가부시키가이샤 | Antistatic agent and resin composition containing same |
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