JPS6326125B2 - - Google Patents

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Publication number
JPS6326125B2
JPS6326125B2 JP4278980A JP4278980A JPS6326125B2 JP S6326125 B2 JPS6326125 B2 JP S6326125B2 JP 4278980 A JP4278980 A JP 4278980A JP 4278980 A JP4278980 A JP 4278980A JP S6326125 B2 JPS6326125 B2 JP S6326125B2
Authority
JP
Japan
Prior art keywords
monomer
acrylate
antistatic
parts
acrylic
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
Application number
JP4278980A
Other languages
Japanese (ja)
Other versions
JPS56139516A (en
Inventor
Katsuaki Maeda
Kohei Ozawa
Junji Seki
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.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
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 Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP4278980A priority Critical patent/JPS56139516A/en
Publication of JPS56139516A publication Critical patent/JPS56139516A/en
Publication of JPS6326125B2 publication Critical patent/JPS6326125B2/ja
Granted legal-status Critical Current

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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アクリル系熱
可塑性樹脂の製造方法に関する。 アクリル系樹脂は、その卓越した透明性、良好
な機械的性質、加工性ならびに成形品の美麗さに
よつて知られ、照明器具、看板、各種装飾品およ
び銘板などに広く使用されている。しかしなが
ら、その表面固有抵抗が非常に高いために、接触
または摩擦等で誘起された静電気が逃散しに
くゝ、そのため使用中の樹脂表面にほこり等が付
着して汚れ易く、美しい外観を損う結果となつて
いる。 従来、合成樹脂の帯電防止法としては、界面活
性剤を中心とした添加練込型とシリコン系化合物
を中心とした表面塗布型に大別される。添加練込
型については、多価アルコールの脂肪酸エステル
等を添加することが提案されているが、ほとんど
効果を示さないか、効果がある場合には、アクリ
ル系樹脂特有の無色透明性、表面光沢の良さが著
しく減じ、実用に供し得ないか、あるいは帯電防
止剤が成型品の表面にブリードして、印刷塗装等
の2次加工性を著しく阻害する。また、表面塗布
型は、一部実用化されているが、最終製品に帯電
防止剤を塗布する工程が必要となり、コスト的に
問題がある。 そこで、本発明者らは、上記の欠点を除去する
ため、アクリル系モノマーと共重合可能なモノマ
ーとのアクリル系共重合体について鋭意検討した
結果、ある特定のアクリル系共重合体が意外にも
良好な帯電防止性能を示し、しかも印刷塗装適性
に優れていることを見い出し、本発明に到つたも
のである。 すなわち、本発明は、メチルメタクリレートお
よび/またはエチルメタクリレートを75%以上、
メチルアクリレート、エチルアクリレート、ブチ
ルアクリレート、スチレン、アクリロニトリルの
1種または2種以上を25%以下含むモノマー
()1部と、一般式 (式中、nは2〜12の整数、Rは炭素数2〜4
の炭化水素基を表わす。) で示されるモノマー()0.01〜0.15部を共重合
することを特徴とする帯電防止能を有するアクリ
ル系熱可塑性樹脂の製造方法である。 本発明のアクリル系モノマー()としては、
メチルメタクリレートおよび/またはエチルメタ
クリレート、および上記モノマーに対し25%以下
のメチルアクリレート、エチルアクリレート、ブ
チルアクリレート、スチレン、アクリロニトリル
の1種または2種以上の混合物を用いることがで
き、好ましくは、メチルメタクリレート75〜99
%、メチルアクリレートあるいはエチルアクリレ
ート1〜25%を含む混合物を用いることができ
る。 また、上記モノマーと共重合可能なモノマー
()としては、一般式 (式中、nは2〜12の整数、Rは炭素数2〜4
の炭化水素基を表わす。) で示されるポリアルキレングリコールモノメタク
リレートを用いることができ、好ましくは、Rが
エチル基、プロピル基またはブチル基であるポリ
アルキレングリコールモノメタクリレートであ
る。 本発明は、モノマー()に対するモノマー
()の比率が1:0.01から1:0.15の割合にお
いて、効果を発揮することができ、特に好ましく
は1:0.02から1:0.10の割合がよい。1:0.01
よりもモノマー()が少ない場合は、帯電防止
効果がない。1:0.15よりモノマー()が多い
場合は、耐熱変形温度が著しく低下し、実用に供
することができない。 また、本発明において、もし必要あれば、組成
物中に他の添加剤、例えば酸化防止剤、滑剤、紫
外線吸収剤、可塑剤および各種の顔料を添加する
こともできる。 本発明による帯電防止能を有するアクリル系樹
脂組成物の製造方法としては、モノマー〔〕、
モノマー〔〕および他の添加剤等を、あらかじ
め混合溶解させ、モノマー相を形成し、重合開始
剤によつて常法通り重合させる方法があるが、そ
の他、連続的に各成分を重合系に添加しつゝ重合
させる方法も可能である。 本発明で製造される樹脂組成物を用いて得られ
る成形品は、計器のメーターカバー、銘板、電気
機器部品等に用いられ、すぐれた帯電防止効果を
発揮することができ、また、銘板等において印刷
塗装等の二次加工性も優れている。 次に実施例により、本発明をさらに具体的に説
明する。 実施例 1 メチルメタクリレート97部に、ポリエチレング
リコールモノメタクリレート(分子量270)3部
を加え、23℃で溶解し、次いでアゾビスイソブチ
ロニトリル0.08部およびステアリルアルコール
0.1部(離型剤)を添加し混合した。このように
して得られた混合物を塩化ビニル製ガスケツトお
よび2枚のガラス板からなる重合用セルに注入
し、80℃で3時間重合を行ない、その後110℃で
1時間熟成した。得られた樹脂板は、一昼夜、恒
温室で状態調整し、帯電防止能を測定した。結果
を表1に示す。帯電防止性能は、比較例1と比較
することにより明らかである。 実施例2〜4、比較例1〜3 モノマー()とモノマー()を表1に示す
ように配合した他は実施例1と同様に重合し、得
られた樹脂板を評価した。結果を表1に示す。
The present invention relates to a method for producing an acrylic thermoplastic resin having antistatic properties. Acrylic resins are known for their outstanding transparency, good mechanical properties, workability, and beautiful molded products, and are widely used in lighting equipment, signboards, various decorative items, nameplates, and the like. However, because the surface resistivity is extremely high, it is difficult for static electricity induced by contact or friction to dissipate, and as a result, the resin surface during use is easily contaminated by dust, etc., spoiling its beautiful appearance. This is the result. Conventionally, antistatic methods for synthetic resins are roughly divided into additive kneading methods using surfactants and surface coating methods using silicone compounds. Regarding the additive kneading type, it has been proposed to add fatty acid esters of polyhydric alcohols, etc., but it has almost no effect, or if it is effective, it does not improve the colorless transparency and surface gloss characteristic of acrylic resins. Either the quality of the molded product is significantly reduced and it cannot be put to practical use, or the antistatic agent bleeds onto the surface of the molded product, significantly inhibiting secondary processability such as printing and painting. In addition, although some surface coating types have been put into practical use, they require a step of applying an antistatic agent to the final product, which poses a problem in terms of cost. Therefore, in order to eliminate the above-mentioned drawbacks, the present inventors conducted intensive studies on acrylic copolymers of acrylic monomers and copolymerizable monomers, and as a result, unexpectedly, a certain acrylic copolymer was found. The inventors have discovered that it exhibits good antistatic performance and is excellent in suitability for printing and coating, leading to the present invention. That is, the present invention provides 75% or more of methyl methacrylate and/or ethyl methacrylate,
1 part of a monomer () containing 25% or less of one or more of methyl acrylate, ethyl acrylate, butyl acrylate, styrene, acrylonitrile, and the general formula (In the formula, n is an integer of 2 to 12, R is a carbon number of 2 to 4
represents a hydrocarbon group. This is a method for producing an acrylic thermoplastic resin having antistatic ability, which comprises copolymerizing 0.01 to 0.15 parts of the monomer ( ) represented by the following formula. The acrylic monomer () of the present invention includes:
Methyl methacrylate and/or ethyl methacrylate, and one or more mixtures of methyl acrylate, ethyl acrylate, butyl acrylate, styrene, acrylonitrile in an amount of up to 25% based on the above monomers, preferably methyl methacrylate 75 ~99
%, methyl acrylate or ethyl acrylate can be used. In addition, monomers () copolymerizable with the above monomers include the general formula (In the formula, n is an integer of 2 to 12, R is a carbon number of 2 to 4
represents a hydrocarbon group. ) A polyalkylene glycol monomethacrylate represented by the following can be used, and preferably a polyalkylene glycol monomethacrylate in which R is an ethyl group, a propyl group, or a butyl group. The present invention can exhibit its effects when the ratio of monomer () to monomer () is from 1:0.01 to 1:0.15, particularly preferably from 1:0.02 to 1:0.10. 1:0.01
If the monomer () is less than , there is no antistatic effect. When the amount of monomer () is more than 1:0.15, the heat deformation resistance temperature decreases significantly and it cannot be put to practical use. In addition, in the present invention, other additives such as antioxidants, lubricants, ultraviolet absorbers, plasticizers, and various pigments may be added to the composition, if necessary. The method for producing the acrylic resin composition having antistatic ability according to the present invention includes monomer [],
There is a method in which the monomer [] and other additives are mixed and dissolved in advance to form a monomer phase, and then polymerized using a polymerization initiator in a conventional manner.Other methods include adding each component continuously to the polymerization system. A method of continuous polymerization is also possible. Molded products obtained using the resin composition produced in the present invention can be used for meter covers, nameplates, electrical equipment parts, etc., and can exhibit excellent antistatic effects, and can also be used in nameplates, etc. It also has excellent secondary processing properties such as printing and painting. Next, the present invention will be explained in more detail with reference to Examples. Example 1 3 parts of polyethylene glycol monomethacrylate (molecular weight 270) was added to 97 parts of methyl methacrylate, dissolved at 23°C, and then 0.08 part of azobisisobutyronitrile and stearyl alcohol were added.
0.1 part (mold release agent) was added and mixed. The mixture thus obtained was poured into a polymerization cell consisting of a vinyl chloride gasket and two glass plates, polymerization was carried out at 80°C for 3 hours, and then aged at 110°C for 1 hour. The obtained resin plate was conditioned in a constant temperature room for one day and night, and its antistatic ability was measured. The results are shown in Table 1. The antistatic performance is clear by comparing with Comparative Example 1. Examples 2 to 4, Comparative Examples 1 to 3 Polymerization was carried out in the same manner as in Example 1, except that monomers () and monomers () were blended as shown in Table 1, and the resulting resin plates were evaluated. The results are shown in Table 1.

【表】 参考例 1 メチルメタクリレート88部、メチルアクリレー
ト2部、グリセリンモノステアレートおよびホウ
酸の等モル混合物10部を混合溶解し、アゾビスイ
ソブチロニトリル0.05重量部を加えた。このよう
にして得られた混合物を用い、実施例1と同様に
して樹脂板を得た。表面固有抵抗は2.0×1011
帯電減衰半減期は4秒であつたが、印刷適性は不
可であつた。
[Table] Reference Example 1 88 parts of methyl methacrylate, 2 parts of methyl acrylate, 10 parts of an equimolar mixture of glycerin monostearate and boric acid were mixed and dissolved, and 0.05 part by weight of azobisisobutyronitrile was added. Using the mixture thus obtained, a resin plate was obtained in the same manner as in Example 1. Surface resistivity is 2.0×10 11 ,
The charge decay half-life was 4 seconds, but the printability was poor.

Claims (1)

【特許請求の範囲】 1 メチルメタクリレートおよび/またはエチル
メタクリレートを75%以上、メチルアクリレー
ト、エチルアクリレート、ブチルアクリレート、
スチレン、アクリロニトリルの1種または2種以
上を25%以下含むモノマー()1部と、一般式 (式中、nは2〜12の整数、Rは炭素数2〜4
の炭化水素基を表わす。) で示されるモノマー()0.01〜0.15部を共重合
することを特徴とする帯電防止能を有するアクリ
ル系熱可塑性樹脂の製造方法。
[Claims] 1 75% or more of methyl methacrylate and/or ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate,
1 part of a monomer () containing 25% or less of one or more of styrene and acrylonitrile, and the general formula (In the formula, n is an integer of 2 to 12, R is a carbon number of 2 to 4
represents a hydrocarbon group. 1. A method for producing an acrylic thermoplastic resin having antistatic properties, which comprises copolymerizing 0.01 to 0.15 parts of a monomer () represented by the following formula.
JP4278980A 1980-04-03 1980-04-03 Antistatic acrylic thermoplastic resin Granted JPS56139516A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4278980A JPS56139516A (en) 1980-04-03 1980-04-03 Antistatic acrylic thermoplastic resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4278980A JPS56139516A (en) 1980-04-03 1980-04-03 Antistatic acrylic thermoplastic resin

Publications (2)

Publication Number Publication Date
JPS56139516A JPS56139516A (en) 1981-10-31
JPS6326125B2 true JPS6326125B2 (en) 1988-05-28

Family

ID=12645726

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4278980A Granted JPS56139516A (en) 1980-04-03 1980-04-03 Antistatic acrylic thermoplastic resin

Country Status (1)

Country Link
JP (1) JPS56139516A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4604414A (en) * 1983-03-31 1986-08-05 Sumitomo Chemical Company, Limited Antistatic acrylic resin composition and method for the production thereof
JPS60229964A (en) * 1984-04-27 1985-11-15 Sekisui Chem Co Ltd Paint for antistatic use

Also Published As

Publication number Publication date
JPS56139516A (en) 1981-10-31

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