JP3862863B2 - Antistatic resin composition - Google Patents

Antistatic resin composition Download PDF

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Publication number
JP3862863B2
JP3862863B2 JP18008598A JP18008598A JP3862863B2 JP 3862863 B2 JP3862863 B2 JP 3862863B2 JP 18008598 A JP18008598 A JP 18008598A JP 18008598 A JP18008598 A JP 18008598A JP 3862863 B2 JP3862863 B2 JP 3862863B2
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Prior art keywords
fatty acid
weight
resin composition
alkyldiethanolamine
antistatic
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JP18008598A
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JP2000007854A (en
Inventor
伸也 後藤
芳治 亀井
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Kao Corp
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Kao Corp
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Description

【0001】
【発明の属する技術分野】
本発明は、帯電防止効果に優れ、かつ高温での帯電防止剤による飛散ガス量を低減化し、更にスリップ性に優れた帯電防止性ポリプロピレン樹脂組成物に関する。
【0002】
【従来の技術及び発明が解決しようとする課題】
ポリプロピレン成形品、特にフィルムにおいては、汚れ付着防止、印刷不良の低減など静電気障害防止の目的で、内部練り込み型帯電防止剤、例えばステアリン酸モノグリセライドに代表されるエステル型帯電防止剤が広く用いられている。
しかし、かかるエステル型帯電防止剤の添加された樹脂を成形する場合、高温に曝されることによって、帯電防止剤の飛散が生じ、環境を汚染したり、ブロー成形、射出成形ではガス抜き穴を塞いでしまいトラブルとなったり、成形不良の発生等が起こり、その及ぼす影響は大きい。
【0003】
高温時の飛散物(発煙物)を減らすためには、一般的にはエステル型帯電防止剤の分子量を大きくする手段が用いられているが、分子量が大きくなると帯電防止効果が得られ難くなり好ましくない。
【0004】
従って、本発明の課題は、帯電防止性やスリップ性を低下させることなく、成形時など高温での飛散ガスの発生を低く押さえ、環境汚染、成形不良等のトラブルを低減できる帯電防止性ポリプロピレン樹脂組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明は、ポリプロピレン樹脂に、下記(A) 成分及び(B) 成分を配合してなる帯電防止性樹脂組成物である。
(A) モノエステル含有量が40〜80重量%、ジエステル含有量が20〜50重量%のグリセリン脂肪酸エステル(但し、エステルを構成する脂肪酸は炭素数12〜22の飽和脂肪酸である)
(B) アルキルジエタノールアミンとアルキルジエタノールアミンの脂肪酸モノエステルとの混合物
【0006】
【発明の実施の形態】
本発明の(A) 成分であるグリセリン脂肪酸エステルとは、グリセリンと炭素数12〜22の飽和脂肪酸とのエステルで、モノエステル含有量が40〜80重量%、ジエステル含有量が20〜50重量%のものである。モノエステル含有量が80重量%を超えると発煙性が大きくなり、また40重量%未満では帯電防止効果の発現に乏しくなる。ジエステル含有量についても20重量%未満であれば、発煙性が大きくなり、50重量%を超えると帯電防止効果の発現が悪くなる。エステルを構成する炭素数12〜22の飽和脂肪酸は、単独でも混合脂肪酸でも良い。
【0007】
本発明の(B) 成分を構成するアルキルジエタノールアミンは、一般式(I)で表される化合物が好ましく、アルキルジエタノールアミンの脂肪酸モノエステルは、一般式(II)で表される化合物が好ましい。
【0008】
【化3】

Figure 0003862863
【0009】
(式中、R1は炭素数12〜22のアルキル基を示す。)
【0010】
【化4】
Figure 0003862863
【0011】
(式中、R2は炭素数12〜22のアルキル基を示し、R3は炭素数11〜21のアルキル基を示す。)
(B) 成分中のアルキルジエタノールアミンとアルキルジエタノールアミンの脂肪酸モノエステルとの重量比は、帯電防止性の観点から40/60以上が好ましく、良好なスリップ性を得るためには60/40以下が好ましい。
【0012】
また、(B) 成分中のアルキルジエタノールアミンと、アルキルジエタノールアミンの脂肪酸モノエステルの原料として用いるアルキルジエタノールアミンのアルキル鎖長は、同一でも異なっていてもよい。
【0013】
本発明の樹脂組成物中の(A) 及び(B) 成分の配合量は、良好な帯電防止効果と低発煙性を達成するためには、ポリプロピレン樹脂に対して、(A) 成分0.2 〜1.0 重量%、(B) 成分 0.2〜1.0 重量%が好ましい。
【0014】
本発明が対象とするポリプロピレン樹脂は、プロピレンのホモポリマー、プロピレンとエチレンとのランダム又はブロックコポリマー等、プロピレンを主体とするものであればいずれの構造のものでも良く、良好な帯電防止効果を発現させることができる。メルトインデックスは、好ましくは0.1 〜20である。
【0015】
本発明の帯電防止性樹脂組成物中には、上記(A) 及び(B) 成分のほか、本発明の効果を阻害しない範囲で、他の樹脂添加剤を併用することができる。
例えばポリオキシエチレン脂肪族アルコール、ポリオキシエチレンアルキルフェニルエーテル、ジヒドロキシエチルアルキルアミド、ポリオキシエチレンアルキルアミド、アルキルスルホン酸塩類等の界面活性剤、エルカ酸アミド、オレイン酸アミド、ポリエチレンワックス、酸化型ポリエチレンワックス、高級アルコール等の滑剤類、2,6−ジ−t−ブチル−4−メチルフェノール、n−オクタデシル−3−(3' ,5' −ジ−t−ブチル−4' −ヒドロキシフェニル)プロピオネート、ペンタエリスリチルテトラキス−〔メチレン−3−(3',5'−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、ジラウリル−3,3' −チオジプロピオネート、ジステアリル−3,3' −チオジプロピオネート、トリスノニルフェニルホスファイト等の酸化防止剤、ビス−(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、〔コハク酸ジメチル−1−(2−ヒドロキシエチル)−4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン〕縮合物等の光安定剤、2−(2' −ヒドロキシ−3' −t−ブチル−5' −メチルフェニル)−5−クロロベンゾトリアゾール等の紫外線吸収剤、ジベンジリデンソルビトール等の造核剤や可塑剤、光安定剤、防曇剤等の添加剤を配合でき、また、他の帯電防止剤等を併用してもよい。
【0016】
本発明の樹脂組成物は、フィルム、シート、ボトル、フィラメント等、あらゆる成形体に成形することができる。
【0017】
【実施例】
以下の例中の部及び%は特記しない限り重量基準である。
【0018】
実施例1〜10及び比較例1〜8
(A) 成分として、表1に示す(A-1)〜(A-5)、(B)成分として、表2に示す(B-1)〜(B-7)を用い、プロピレン重合体〔(株)グランドポリマー社のFー122V〕100部に対し、表3に示す量を配合し、更に酸化防止剤としてペンタエリスリチルテトラキス−〔メチレン−3−(3’,5’−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネートを0.1 部、ステアリン酸カルシウム0.05部を配合し、タンブラーで混合後、210 ℃に調整した二軸押出機でペレットを得た。次にこのペレットから280 ℃に調整したT−ダイ製膜装置により厚み100 ミクロンのフィルムを成形し、試料とした。
この試料を用い、下記方法で表面固有抵抗値及び動摩擦係数を測定し、発煙性を評価した。結果を表3に示す。
【0019】
【表1】
Figure 0003862863
【0020】
【表2】
Figure 0003862863
【0021】
<表面固有抵抗値の測定法>
100ミクロンに成形したフィルムを、温度25℃、湿度50%RHの室内に7日間保管の後、横河ヒューレットパッカード社のハイレジスタンスメータA−3941型にて表面固有抵抗値(Ω)を測定した。
【0022】
<動摩擦係数の測定法>
100ミクロンに成形したフィルムを23℃の室内に7日間保管の後、JIS K-7125に準じ、動摩擦係数を測定した。
【0023】
<発煙性の評価法>
280℃T−ダイによるフィルム成形時、目視にて発煙の評価を行った。発煙が全く見えない場合には◎評価とし、発煙が少なく僅かに見える程度を○評価とし、白煙として確認できる場合には×評価とした。
【0024】
【表3】
Figure 0003862863
【0025】
表面固有抵抗値は1×1013Ω未満では実用上問題ないレベルであり、動摩擦係数は低いほどスリップ性が良好なことを意味し、0.5 以下で実用上問題ないレベルであるが、表3より、実施例1〜10はいずれも表面固有抵抗値が小さく帯電防止性に優れ、かつ良好なスリップ性を示し、発煙性についてもその防止効果が高いことが明らかである。
一方、比較例1〜8は、表面固有抵抗値、動摩擦係数、発煙性の評価結果から帯電防止性、スリップ性及び発煙防止性のすべてを同時に満足できないことが明らかである。
【0026】
【発明の効果】
本発明の帯電防止性樹脂組成物をポリプロピレン樹脂に添加することにより、帯電防止効果やスリップ性を低下させることなく成形時の発煙防止が達成でき、作業環境を改善することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antistatic polypropylene resin composition which has an excellent antistatic effect, reduces the amount of scattered gas due to an antistatic agent at high temperatures, and further has excellent slip properties.
[0002]
[Prior art and problems to be solved by the invention]
In polypropylene molded products, especially films, internal kneading type antistatic agents, such as ester type antistatic agents typified by stearic acid monoglyceride, are widely used for the purpose of preventing electrostatic damage such as prevention of dirt adhesion and printing defects. ing.
However, when molding a resin to which such an ester-type antistatic agent is added, the antistatic agent is scattered by exposure to high temperatures, contaminating the environment, and in blow molding and injection molding, vent holes are formed. Occurrence of clogging will cause troubles and occurrence of molding defects, etc., and the effect will be great.
[0003]
In order to reduce scattered matter (smoke matter) at high temperatures, generally means for increasing the molecular weight of the ester type antistatic agent is used, but it is difficult to obtain an antistatic effect when the molecular weight is increased, which is preferable. Absent.
[0004]
Therefore, an object of the present invention is to provide an antistatic polypropylene resin that can suppress the generation of scattered gas at a high temperature such as molding and reduce troubles such as environmental pollution and molding defects without deteriorating the antistatic property and slip property. It is to provide a composition.
[0005]
[Means for Solving the Problems]
The present invention is an antistatic resin composition obtained by blending the following components (A) and (B) with a polypropylene resin.
(A) Glycerin fatty acid ester having a monoester content of 40 to 80% by weight and a diester content of 20 to 50% by weight (however, the fatty acid constituting the ester is a saturated fatty acid having 12 to 22 carbon atoms)
(B) Mixture of alkyldiethanolamine and fatty acid monoester of alkyldiethanolamine [0006]
DETAILED DESCRIPTION OF THE INVENTION
The glycerin fatty acid ester as the component (A) of the present invention is an ester of glycerin and a saturated fatty acid having 12 to 22 carbon atoms, the monoester content is 40 to 80% by weight, and the diester content is 20 to 50% by weight. belongs to. When the monoester content exceeds 80% by weight, the smoke generation becomes large, and when it is less than 40% by weight, the antistatic effect is poorly exhibited. If the diester content is less than 20% by weight, the fuming property is increased. If the diester content exceeds 50% by weight, the antistatic effect is deteriorated. The saturated fatty acid having 12 to 22 carbon atoms constituting the ester may be a single fatty acid or a mixed fatty acid.
[0007]
The alkyldiethanolamine constituting the component (B) of the present invention is preferably a compound represented by the general formula (I), and the fatty acid monoester of the alkyldiethanolamine is preferably a compound represented by the general formula (II).
[0008]
[Chemical 3]
Figure 0003862863
[0009]
(In the formula, R 1 represents an alkyl group having 12 to 22 carbon atoms.)
[0010]
[Formula 4]
Figure 0003862863
[0011]
(In the formula, R 2 represents an alkyl group having 12 to 22 carbon atoms, and R 3 represents an alkyl group having 11 to 21 carbon atoms.)
In the component (B), the weight ratio between the alkyldiethanolamine and the fatty acid monoester of alkyldiethanolamine is preferably 40/60 or more from the viewpoint of antistatic properties, and preferably 60/40 or less in order to obtain good slip properties.
[0012]
In addition, the alkyl chain length of the alkyldiethanolamine in the component (B) and the alkyldiethanolamine used as a raw material for the fatty acid monoester of the alkyldiethanolamine may be the same or different.
[0013]
The blending amount of the components (A) and (B) in the resin composition of the present invention is such that the component (A) is 0.2 to 1.0 with respect to the polypropylene resin in order to achieve a good antistatic effect and low smoke generation. % By weight and (B) component 0.2 to 1.0% by weight are preferred.
[0014]
The polypropylene resin targeted by the present invention may have any structure as long as it is mainly composed of propylene, such as a homopolymer of propylene, a random or block copolymer of propylene and ethylene, and exhibits a good antistatic effect. Can be made. The melt index is preferably 0.1-20.
[0015]
In the antistatic resin composition of the present invention, in addition to the components (A) and (B), other resin additives can be used in combination as long as the effects of the present invention are not impaired.
For example, surfactants such as polyoxyethylene aliphatic alcohol, polyoxyethylene alkylphenyl ether, dihydroxyethyl alkylamide, polyoxyethylene alkylamide, alkyl sulfonates, erucic acid amide, oleic acid amide, polyethylene wax, oxidized polyethylene Lubricants such as wax and higher alcohol, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate , Pentaerythrityltetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate], dilauryl-3,3′-thiodipropionate, distearyl-3,3 '-Thiodipropionate, trisnonylphenylphospho Antioxidants such as phyto, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, [dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6 succinate , 6-tetramethylpiperidine] condensate, etc., UV stabilizers such as 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, dibenzylidene Nucleating agents such as sorbitol, additives such as plasticizers, light stabilizers and antifogging agents can be added, and other antistatic agents and the like may be used in combination.
[0016]
The resin composition of the present invention can be formed into any molded body such as a film, a sheet, a bottle, and a filament.
[0017]
【Example】
Parts and% in the following examples are based on weight unless otherwise specified.
[0018]
Examples 1-10 and Comparative Examples 1-8
(A) As components (A-1) to (A-5) shown in Table 1, and (B) as components (B-1) to (B-7) shown in Table 2 as propylene polymers [ The amount shown in Table 3 is blended with 100 parts of F-122V of Grand Polymer Co., Ltd., and pentaerythrityltetrakis- [methylene-3- (3 ′, 5′-di-t] as an antioxidant. -Butyl-4-hydroxyphenyl) propionate (0.1 part) and calcium stearate (0.05 part) were blended, mixed with a tumbler, and then pellets were obtained with a twin screw extruder adjusted to 210 ° C. Next, a film having a thickness of 100 microns was formed from this pellet by a T-die film forming apparatus adjusted to 280 ° C., and used as a sample.
Using this sample, the surface specific resistance value and the dynamic friction coefficient were measured by the following method to evaluate the fuming property. The results are shown in Table 3.
[0019]
[Table 1]
Figure 0003862863
[0020]
[Table 2]
Figure 0003862863
[0021]
<Measurement method of surface resistivity>
The film formed to 100 microns was stored for 7 days in a room with a temperature of 25 ° C. and a humidity of 50% RH, and then the surface resistivity (Ω) was measured with a high resistance meter A-3941 of Yokogawa Hewlett-Packard Company. .
[0022]
<Measuring method of dynamic friction coefficient>
The film molded to 100 microns was stored in a room at 23 ° C. for 7 days, and the dynamic friction coefficient was measured according to JIS K-7125.
[0023]
<Smoke evaluation method>
At the time of film formation with a 280 ° C. T-die, smoke was visually evaluated. When the smoke generation was not seen at all, it was evaluated as 、, the extent of the slight smoke generation and slightly visible was rated as ○, and when it could be confirmed as white smoke, it was rated as 評 価.
[0024]
[Table 3]
Figure 0003862863
[0025]
The surface resistivity value is less than 1 × 10 13 Ω for practical use. The lower the dynamic friction coefficient, the better the slip performance. The value of 0.5 or less is practical for practical use. It is clear that Examples 1 to 10 all have a small surface specific resistance value, excellent antistatic properties, good slip properties, and high smoke prevention properties.
On the other hand, it is clear that Comparative Examples 1 to 8 cannot satisfy all of the antistatic property, the slip property, and the smoke prevention property simultaneously from the evaluation results of the surface specific resistance value, the dynamic friction coefficient, and the smoke emission property.
[0026]
【The invention's effect】
By adding the antistatic resin composition of the present invention to a polypropylene resin, smoke prevention during molding can be achieved without lowering the antistatic effect and slipping property, and the working environment can be improved.

Claims (4)

ポリプロピレン樹脂に、下記(A) 成分及び(B) 成分を配合してなる帯電防止性樹脂組成物。
(A) モノエステル含有量が40〜80重量%、ジエステル含有量が20〜50重量%のグリセリン脂肪酸エステル(但し、エステルを構成する脂肪酸は炭素数12〜22の飽和脂肪酸である)
(B) アルキルジエタノールアミンとアルキルジエタノールアミンの脂肪酸モノエステルとの混合物
An antistatic resin composition comprising a polypropylene resin and the following components (A) and (B):
(A) Glycerin fatty acid ester having a monoester content of 40 to 80% by weight and a diester content of 20 to 50% by weight (however, the fatty acid constituting the ester is a saturated fatty acid having 12 to 22 carbon atoms)
(B) Mixture of alkyldiethanolamine and fatty acid monoester of alkyldiethanolamine
(B) 成分中のアルキルジエタノールアミンとアルキルジエタノールアミンの脂肪酸モノエステルとの重量比が、40/60〜60/40である請求項1記載の帯電防止性樹脂組成物。  The antistatic resin composition according to claim 1, wherein the weight ratio of the alkyl diethanolamine and the fatty acid monoester of alkyl diethanolamine in the component (B) is 40/60 to 60/40. アルキルジエタノールアミンが一般式(I)で表される化合物であり、アルキルジエタノールアミンの脂肪酸モノエステルが一般式(II)で表される化合物である請求項1又は2記載の帯電防止性樹脂組成物。
Figure 0003862863
(式中、R1は炭素数12〜22のアルキル基を示す。)
Figure 0003862863
(式中、R2は炭素数12〜22のアルキル基を示し、R3は炭素数11〜21のアルキル基を示す。)
3. The antistatic resin composition according to claim 1, wherein the alkyldiethanolamine is a compound represented by the general formula (I), and the fatty acid monoester of the alkyldiethanolamine is a compound represented by the general formula (II).
Figure 0003862863
(In the formula, R 1 represents an alkyl group having 12 to 22 carbon atoms.)
Figure 0003862863
(In the formula, R 2 represents an alkyl group having 12 to 22 carbon atoms, and R 3 represents an alkyl group having 11 to 21 carbon atoms.)
ポリプロピレン樹脂に対する (A)成分の配合量が 0.2〜1.0 重量%、(B) 成分の配合量が 0.2〜1.0 重量%である請求項1〜3のいずれか一項に記載の帯電防止性樹脂組成物。The antistatic resin composition according to any one of claims 1 to 3, wherein the blending amount of the component (A) with respect to the polypropylene resin is 0.2 to 1.0% by weight, and the blending amount of the component (B) is 0.2 to 1.0% by weight. object.
JP18008598A 1998-06-26 1998-06-26 Antistatic resin composition Expired - Fee Related JP3862863B2 (en)

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