JPH0548254B2 - - Google Patents

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Publication number
JPH0548254B2
JPH0548254B2 JP1494284A JP1494284A JPH0548254B2 JP H0548254 B2 JPH0548254 B2 JP H0548254B2 JP 1494284 A JP1494284 A JP 1494284A JP 1494284 A JP1494284 A JP 1494284A JP H0548254 B2 JPH0548254 B2 JP H0548254B2
Authority
JP
Japan
Prior art keywords
weight
resin
parts
formula
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP1494284A
Other languages
Japanese (ja)
Other versions
JPS60158242A (en
Inventor
Tetsuya Niimura
Sadanobu Kato
Hidehiko Takizawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP1494284A priority Critical patent/JPS60158242A/en
Publication of JPS60158242A publication Critical patent/JPS60158242A/en
Publication of JPH0548254B2 publication Critical patent/JPH0548254B2/ja
Granted legal-status Critical Current

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Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は帯電防止性能を有するメタクリル酸メ
チル・スチレン系樹脂組成物に関するものであ
る。 メタクリル酸メチル・スチレン系樹脂(以下
MS樹脂と呼ぶ)は、その透明性、着色時の光沢
及び外観の美しさのためにオーデイオ類の銘板、
事務機器の銘板及び照明器具等に使用されている
が、その表面固有抵抗が非常に高いため帯電しや
すい性質を有しており、帯電によるごみ、ほこり
の付着のため外観がそこなわれることがしばしば
起こる。 従来、合成樹脂の帯電防止法としては、界面活
性剤等の添加剤を添加して練込む添加練込法と、
シリコン系化合物等を製品の表面に塗布する表面
塗布法が知られている。しかしながら、添加練込
法では、ポリスチレン樹脂に対しては帯電防止効
果がある添加剤をMS樹脂に適用しても効果が十
分でなかつたり、透明性を阻害し満足すべきもの
は見当らない。また、帯電防止能が認められるま
で添加剤の添加量を増加すると、 MS樹脂本来の物性、特に耐熱性、熱安定性及
び強度の低下等を伴ない、実用に供することがで
きない。表面塗布法としては、例えば、スタテイ
サイド(商品名、Analytical Chemical
Laboratories社製)が効果を示すが、塗布後水洗
すると効果が失われ、永久性に乏しいうえ、コス
ト的に問題があり、優れた方法とは言えない。 またアクリル系樹脂組成物に帯電防止性能を付
与するために、アクリル系樹脂に高級脂脂肪酸グ
リセライドとポリアルキレングリコール及び燐化
合物を添加する方法(特開昭51−49246)及びグ
リセリンモノ脂肪酸エステルとアルキルスルホン
酸ソーダを添加する方法(特開昭58−125741)が
提案されているが、このいずれの方法をMS樹脂
に適用しても顕著な効果は認められない。 本発明者は帯電防止性能を有するMS樹脂を得
るべく鋭意検討した結果、本発明に達したもので
あり、高級脂肪酸モノグリセライドと特定の二級
アミンを併用添加することにより、少量の配合量
で、優れた帯電防止効果をもち、かつ機械的性質
及び熱的性質のバランスがよいMS樹脂を得るこ
とができたのである。 すなわち本発明は、MS樹脂100重量部に対し
高級脂肪酸モノグリセライド1.0〜4.0重量部及び
式(1)で示される二級アミン1.0〜3.0重量部を含む
ことを特徴とする帯電防止性の優れた樹脂組成物
に関するものである。 式(1) (但し、R1は脂肪族、脂環族又は芳香族の炭化
水素基であり、R2はC1〜C8のアルキレン基であ
る。) 式(1)においてR1がC12〜C18の直鎖アルキル基
であり、R2がCH2CH2である二級アミンが特に
好ましく使われる。 高級脂肪酸モノグリセライドを単独でMS樹脂
に添加した場合にはMS樹脂100重量部に対し10
重量部添加しても、製品の表面固有抵抗値はほと
んど低下せず、帯電防止効果は十分でなかつた。 また、式(1)で示した特定の二級アミンを単独で
用いた場合にはMS樹脂100重量部に対し10重量
部添加すると、表面固有抵抗値は109オームまで
低下し良好な帯電防止効果を示したが、MS樹脂
の耐熱性を著しく低下させ、さらには黄変が激し
く、実用に供しえないものとなつた。ところが、
高級脂肪酸モノグリセライドと式(1)で示した特定
の二級アミンをそれぞれ上記の量併用添加した場
合には、単独添加の場合に比べて必要とされる全
添加量を減じることができ、物性上も好ましい帯
電防止性MS樹脂を得ることができた。 本発明の組成物を構成する高級樹脂酸モノグリ
セライドとしては、例えばラウリン酸、パルミチ
ン酸、ステリアン酸、モンタン酸、オレイン酸、
リノール酸及びベヘニン酸などのモノグリセライ
ドがあげられる。通常これらには、ジグリセライ
ド、トリグリセライドが少量含まれているが、モ
ノグリセライドが90重量%以上の高純度のものが
好ましい。純度が低いと少量の添加でもMS樹脂
の透明性を阻害することがある。高級脂肪酸モノ
グリセライドの添加量は、MS樹脂100重量部に
対して1.0〜4.0重量部である。1.0重量部より少量
では帯電防止効果が乏しく、4.0重量部を超えて
用いた場合にはMS樹脂の物性、特に耐熱性の低
下が著しく、さらには白濁を生じ著しく透明性を
そこなうことがある。 本発明の組成物を構成する式(1)で示される二級
アミンの添加量はMS樹脂100重量部に対して1.0
〜3.0重量部である。1.0重量部より少量では帯電
防止効果が乏しく、3.0重量部を超えて用いた場
合にはMS樹脂の物性、特に耐熱性の低下が著し
く、さらには黄変が激しく製品として使用に耐え
なくなる。 本発明で言うMS樹脂とは、メタクリル酸メチ
ル20重量%以上及びスチレン20重量%以上含みか
つ両者の合計が50重量%以上からなる共重合体、
メタクリル酸メチル20重量%以上及びスチレン誘
導体−例えばα−メチルスチレンのようなα置換
スチレン、p−メチルスチレンのような核置換ス
チレンを20重量%以上含み、かつ両者の合計が50
重量%以上からなる共重合体、さらに上記モノマ
ーの組成を必須成分として、さらに共重合可能な
アクリル酸エステル、メタクリル酸エステル、ア
クリロニトリルなどのモノマーをその一種以上共
重合した共重合体、並びにこれらの共重合体に合
成ゴムを混合又はグラフトのような化学的結合の
形で含有した重合体を意味する。これらのMS樹
脂は、塊状重合法、溶液重合法、乳化重合法、懸
濁重合法又は塊状−懸濁重合法等通常知られてい
る重合方法によつて得ることができる。 本発明の組成物はMS樹脂、高級脂肪酸モノグ
リセライド及び式(1)で示される二級アミンを押出
機などで溶融混練することにより得ることができ
る。また、高級脂肪酸モノグリセライドをMS樹
脂の重合の際に原料モノマーに添加し重合して得
られたポリマーに式(1)で示される二級アミンを押
出機などで溶融混練する方法でも得ることができ
る。 このようにして得られる本発明のMS樹脂組成
物を射出成形、押出成形等の成形法で成形して得
られた成形品は表面固有抵抗値が小さく、帯電減
衰半減期も短かく、優れた帯電防止性を示す。成
形品としては、家電製品の銘板類、メーターカバ
ー、IC関連ケース類、OA機器のカバー、ケース
類等が挙げられる。 本発明の組成物において通常使用される添加
剤、例えば可塑剤、安定剤、着色剤等を添加して
もさしつかえない。 以下、実施例及び比較例を挙げて本発明を具体
的に説明する。 実施例1〜9、比較例1〜5 メタクリル酸メチル50重量%とスチレン50重通
%からなる重量平均分子量15万のMS樹脂のビー
ズ100重量部に、ステアリン酸モノグリセライド
(商品名リケマールS100A、理研ビタミン社製)
および式(1)で示される二級アミン(式(1)において
R2がCH2CH2で、R1がC12のアルキル基のものと
C14のアルキル基のものの混合物である。商品名
ダスパー125B、ミヨシ油脂社製)を表−1に示
した各種割合で添加し、40mmφ押出機を用いて、
200℃にて溶融混練し、ペレツトとした。得られ
たペレツトを2オンス射出成形機を用いて、シリ
ンダー温度230℃金型温度40℃にて40mm×40mm×
2mmの平板を射出成形して得た。 得られた平板について、帯電防止性能を測定し
た。結果を表−1にまとめて示す。
The present invention relates to a methyl methacrylate/styrene resin composition having antistatic properties. Methyl methacrylate/styrene resin (hereinafter
MS resin) is used as a nameplate for audio products due to its transparency, gloss when colored, and beautiful appearance.
It is used for nameplates of office equipment, lighting equipment, etc., but because its surface resistivity is extremely high, it is easily charged with electricity, and its appearance may be damaged due to the adhesion of dirt and dust due to electrostatic charge. Happens often. Conventionally, antistatic methods for synthetic resins include additive kneading methods in which additives such as surfactants are added and kneaded;
A surface coating method is known in which a silicon-based compound or the like is applied to the surface of a product. However, in the additive kneading method, even if additives that have an antistatic effect on polystyrene resin are applied to MS resin, the effect is not sufficient or the transparency is impaired, so no satisfactory additives have been found. Furthermore, if the amount of additives added is increased until antistatic ability is observed, the inherent physical properties of the MS resin, particularly heat resistance, thermal stability, and strength, will decrease, making it impossible to put it to practical use. As a surface coating method, for example, Statyside (trade name, Analytical Chemical
Laboratories) is effective, but it loses its effectiveness when washed with water after application, is not permanent, and is costly, so it cannot be considered an excellent method. In addition, in order to impart antistatic properties to acrylic resin compositions, there is a method of adding higher fatty acid glycerides, polyalkylene glycols, and phosphorus compounds to acrylic resins (Japanese Patent Application Laid-open No. 51-49246), and a method of adding glycerin monofatty acid esters and alkyl A method of adding sodium sulfonate (Japanese Patent Laid-Open No. 125741/1983) has been proposed, but no significant effect has been observed when either of these methods is applied to MS resin. The inventor of the present invention has arrived at the present invention as a result of intensive studies to obtain an MS resin with antistatic properties.By adding higher fatty acid monoglyceride and a specific secondary amine in combination, a small amount of MS resin can be obtained. We were able to obtain an MS resin that has an excellent antistatic effect and a good balance of mechanical and thermal properties. That is, the present invention provides a resin with excellent antistatic properties, which contains 1.0 to 4.0 parts by weight of higher fatty acid monoglyceride and 1.0 to 3.0 parts by weight of a secondary amine represented by formula (1) per 100 parts by weight of MS resin. The present invention relates to a composition. Formula (1) (However, R 1 is an aliphatic, alicyclic, or aromatic hydrocarbon group, and R 2 is a C 1 to C 8 alkylene group.) In formula (1), R 1 is a C 12 to C 18 Secondary amines in which R 2 is CH 2 CH 2 are particularly preferably used. When higher fatty acid monoglyceride is added alone to MS resin, the amount is 10% per 100 parts by weight of MS resin.
Even when part by weight was added, the surface resistivity value of the product hardly decreased, and the antistatic effect was not sufficient. In addition, when the specific secondary amine shown in formula (1) is used alone, when 10 parts by weight is added to 100 parts by weight of MS resin, the surface resistivity value decreases to 10 9 ohms, resulting in good antistatic properties. Although it was effective, it significantly lowered the heat resistance of the MS resin and caused severe yellowing, making it unsuitable for practical use. However,
When higher fatty acid monoglyceride and the specific secondary amine shown in formula (1) are added together in the above amounts, the total amount required can be reduced compared to when they are added alone, and the physical properties are improved. It was also possible to obtain a preferable antistatic MS resin. Examples of the higher resin acid monoglyceride constituting the composition of the present invention include lauric acid, palmitic acid, stearic acid, montanic acid, oleic acid,
Examples include monoglycerides such as linoleic acid and behenic acid. These usually contain small amounts of diglycerides and triglycerides, but highly pure ones containing 90% by weight or more of monoglycerides are preferred. If the purity is low, the transparency of MS resin may be inhibited even when added in small amounts. The amount of higher fatty acid monoglyceride added is 1.0 to 4.0 parts by weight per 100 parts by weight of MS resin. If the amount is less than 1.0 parts by weight, the antistatic effect will be poor, and if it is used in excess of 4.0 parts by weight, the physical properties of the MS resin, especially the heat resistance, will be significantly reduced, and furthermore, it may become cloudy and significantly impair its transparency. The amount of secondary amine represented by formula (1) constituting the composition of the present invention is 1.0 parts by weight per 100 parts by weight of MS resin.
~3.0 parts by weight. If the amount is less than 1.0 part by weight, the antistatic effect will be poor, and if it is used in excess of 3.0 parts by weight, the physical properties of the MS resin, especially the heat resistance, will be significantly reduced, and yellowing will be so severe that it will become unusable as a product. The MS resin referred to in the present invention is a copolymer containing 20% by weight or more of methyl methacrylate and 20% by weight or more of styrene, and the total of both is 50% by weight or more.
Contains 20% by weight or more of methyl methacrylate and styrene derivatives such as α-substituted styrene such as α-methylstyrene, or nuclear-substituted styrene such as p-methylstyrene, and the total of both is 50% by weight.
% or more by weight, and copolymers in which the composition of the above monomers is an essential component and one or more copolymerizable monomers such as acrylic ester, methacrylic ester, acrylonitrile, etc. are copolymerized, and these. It refers to a copolymer containing synthetic rubber in the form of a chemical bond such as mixing or grafting. These MS resins can be obtained by commonly known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization. The composition of the present invention can be obtained by melt-kneading MS resin, higher fatty acid monoglyceride, and a secondary amine represented by formula (1) using an extruder or the like. It can also be obtained by adding higher fatty acid monoglyceride to the raw material monomer during polymerization of MS resin and melt-kneading the secondary amine represented by formula (1) with the polymer obtained by polymerization using an extruder etc. . Molded products obtained by molding the MS resin composition of the present invention obtained in this manner by a molding method such as injection molding or extrusion molding have a small surface resistivity value, a short charge decay half-life, and have excellent properties. Shows antistatic properties. Examples of molded products include nameplates for home appliances, meter covers, IC-related cases, covers and cases for OA equipment, etc. Additives commonly used in the compositions of the invention, such as plasticizers, stabilizers, colorants, etc., may be added. Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Examples 1 to 9, Comparative Examples 1 to 5 Stearic acid monoglyceride (trade name Rikemar S100A, Riken (manufactured by Vitamin Co.)
and a secondary amine represented by formula (1) (in formula (1)
R 2 is CH 2 CH 2 and R 1 is a C 12 alkyl group.
It is a mixture of C14 alkyl groups. (trade name: Dasper 125B, manufactured by Miyoshi Oil Co., Ltd.) was added in various proportions shown in Table 1, and using a 40 mmφ extruder,
The mixture was melted and kneaded at 200°C to form pellets. Using a 2-ounce injection molding machine, the obtained pellets were molded into 40 mm × 40 mm × cylinder temperature of 230 °C and mold temperature of 40 °C.
A 2 mm flat plate was obtained by injection molding. The antistatic performance of the obtained flat plate was measured. The results are summarized in Table-1.

【表】 表−1から本発明による樹脂組成物の帯電防止
性能は良好であり、かつ商品として十分実用に供
する外観を有していることがわかる。 実施例 10 メタクリル酸メチル57.5重量部及びスチレン
42.5重量部からなる単量体混合物に、この単量体
混合物と屈折率の一致するスチレン−ブタジエン
ゴムを5重量部グラフト重合させて製造したMS
樹脂100重量部に、ステアリン酸モノグリセライ
ド(商品名リケマールS100A、理研ビタミン社
製)を3重量部および式(1)で示される二級アミン
(式(1)においてR2がCH2CH2で、R1がC12のアル
キル基のものとC14のアルキル基のものの混合物
である。商品名、ダスパー125B、ミヨシ油脂社
製)を2重量部添加し、40mmφ押出機を用いて
200℃にて溶融混練し、ペレツトとした。得られ
たペレツトを2オンス射出成形機を用いて、シリ
ンダー温度230℃、金型温度10℃にて40mm×40mm
×2mmの平板を射出成形して得た。得られた平板
の表面固有抵抗値は8×109Ω、帯電減衰半減期
は3秒であつた。また、平板は薄黄色で完全に透
旧であつた。 比較例 6 実施例10において、MS樹脂にステアリン酸モ
ノグリセライド及び式(1)で示される二級アミンを
添加しない場合は表面固有抵抗値は1×1016Ω、
帯電減衰半減期は無限大であつた。
[Table] From Table 1, it can be seen that the resin composition according to the present invention has good antistatic performance and has an appearance that can be used practically as a commercial product. Example 10 57.5 parts by weight of methyl methacrylate and styrene
MS produced by graft polymerizing 5 parts by weight of styrene-butadiene rubber whose refractive index matches that of this monomer mixture to a monomer mixture consisting of 42.5 parts by weight.
To 100 parts by weight of the resin, 3 parts by weight of stearic acid monoglyceride (trade name Rikemar S100A, manufactured by Riken Vitamin Co., Ltd.) and a secondary amine represented by formula (1) (in formula (1), R 2 is CH 2 CH 2 , It is a mixture of an alkyl group in which R 1 is C 12 and an alkyl group in C 14. 2 parts by weight of Dasper 125B (trade name, manufactured by Miyoshi Oil Co., Ltd.) are added, and the mixture is made using a 40 mmφ extruder.
The mixture was melted and kneaded at 200°C to form pellets. The obtained pellets were molded into 40mm x 40mm using a 2oz injection molding machine at a cylinder temperature of 230℃ and a mold temperature of 10℃.
A 2 mm x 2 mm flat plate was obtained by injection molding. The surface resistivity value of the obtained flat plate was 8×10 9 Ω, and the charge decay half-life was 3 seconds. In addition, the flat plate was pale yellow and completely old. Comparative Example 6 In Example 10, when stearic acid monoglyceride and the secondary amine represented by formula (1) are not added to the MS resin, the surface specific resistance value is 1 × 10 16 Ω,
The charge decay half-life was infinite.

Claims (1)

【特許請求の範囲】 1 メタクリル酸メチル−スチレン系樹脂100重
量部に対し高級脂肪酸モノグリセライド1.0〜4.0
重量部及び式(1)で示される二級アミン1.0〜3.0重
量部を含むことを特徴とする樹脂組成物。 式(1) (但し、R1は脂肪族、脂環族又は芳香族の炭化
水素基であり、R2はC1〜C8のアルキレン基であ
る。)
[Claims] 1. 1.0 to 4.0 of higher fatty acid monoglyceride per 100 parts by weight of methyl methacrylate-styrene resin.
1. A resin composition comprising 1.0 to 3.0 parts by weight of a secondary amine represented by formula (1). Formula (1) (However, R 1 is an aliphatic, alicyclic, or aromatic hydrocarbon group, and R 2 is a C 1 to C 8 alkylene group.)
JP1494284A 1984-01-30 1984-01-30 Resin composition Granted JPS60158242A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1494284A JPS60158242A (en) 1984-01-30 1984-01-30 Resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1494284A JPS60158242A (en) 1984-01-30 1984-01-30 Resin composition

Publications (2)

Publication Number Publication Date
JPS60158242A JPS60158242A (en) 1985-08-19
JPH0548254B2 true JPH0548254B2 (en) 1993-07-21

Family

ID=11875011

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1494284A Granted JPS60158242A (en) 1984-01-30 1984-01-30 Resin composition

Country Status (1)

Country Link
JP (1) JPS60158242A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2166949A1 (en) * 1995-01-12 1996-07-13 Dan Zimmerman Substantially transparent antistatic acrylic polymer

Also Published As

Publication number Publication date
JPS60158242A (en) 1985-08-19

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