JP2006016449A - Antistatic polyolefin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inexpensively provide an antistat for a polyolefin film which assures suitable printability on the film using any printing ink among organic solvent-based inks and aqueous inks, imparts excellent antistaticity, hardly causes whitening by bleeding with time and gives excellent transparency. <P>SOLUTION: The antistat comprises an amine ester compound obtained by reacting 0.8-1.5 mole of an 8-22C straight chain or branched fatty acid and/or a derivative thereof with 1 mole of at least one tertiary amine represented by general formula (A), where at least 10 wt% of the amine ester compound comprises an ester compound of a tertiary amine bearing an unsaturated bond where R<SB>1</SB>is bivalent or higher-valent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is suitable for both organic solvent-based inks and water-based inks having conflicting liquid properties, and can be used to obtain an antistatic polyolefin film with little bleeding whitening over time and excellent transparency. The present invention relates to an inhibitor and a polyolefin film containing the antistatic agent and printed with water-based ink or organic solvent-based ink.

  Polyolefin films are widely used for product packaging and are very important for product manufacturers, and it is required to increase the value of products such as making the contents easier to see by improving the transparency of the film. ing.

  In such applications, printing is usually performed on the surface with printing ink, and methods such as screen printing, flexographic printing, offset printing, and gravure printing are used for printing on the surface of the polyolefin film.

  In general, a method of adding an antistatic agent to polyolefin film in advance to prevent dust adhesion and the generation of static electricity during film processing is generally performed, but the antistatic agent is bleed on the film surface. Otherwise, the effect cannot be obtained, but on the other hand, since the bleed antistatic agent exists between the printing ink and the film, the transfer property of the printing ink to the film is deteriorated, and further, the transparency of the film due to excessive bleed. May cause quality problems.

  As methods for improving the printability of organic solvent-based inks or water-based inks in this polyolefin film, Patent Literature 1, Patent Literature 2, and Patent Literature 3 disclose methods using amide type antistatic agents. Patent Document 4 discloses a method of adding a mixture of an amide antistatic agent and a polyhydric alcohol fatty acid ester.

  From the prior art, various physical properties such as printing suitability, antistatic property, and transparency for any printing ink of organic solvent-based ink and water-based ink, which are not necessarily compatible with liquid properties required for polyolefin films, are sufficiently satisfied. However, there was a need for further improvements.

JP-A-1-287157 (pages 1-7) JP-A-6-345904 (page 1-9) JP-A-7-164608 (page 1-6) JP-A-10-235816 (pages 1-7)

  The object of the present invention is that the printing property on the film is suitable for any printing ink of organic solvent-based ink and water-based ink whose liquidity is opposite to that of the polyolefin film, excellent in antistatic properties, and bleed whitening over time. It is to provide an antistatic agent with a small amount and excellent transparency at low cost. Furthermore, the object of the present invention is to provide a polyolefin resin composition containing such an antistatic agent, a polyolefin film comprising the resin composition, and particularly an organic solvent ink and water-based ink in which at least one surface of the film is in conflict with liquidity. It is an object of the present invention to provide an antistatic polyolefin film which is printed with any printing ink.

（Ｒ₁は直鎖もしくは分岐鎖の炭素数８〜２２の、アルキル基、アルケニル基、ヒドロキシアルキル基又はヒドロキシアルケニル基であり、ｍ及びｎは１又は２の整数であり、且つ、ｍ＋ｎは２又は３である。）
また本発明は、かかる帯電防止剤をポリオレフィン樹脂に対し０.１〜２.０重量％含有することを特徴とする、ポリオレフィン樹脂組成物にも関する。
さらに本発明は、前述のポリオレフィン樹脂組成物からなるポリオレフィンフィルム、特にその中で、少なくとも一方の表面が、有機溶剤系インキ及び／又は水系インキで印刷されているところのポリオレフィンフィルムにもまた関する。 As a result of diligent research to solve the above-mentioned problems, the present inventors used an amine ester compound obtained by reacting a tertiary amine having a unsaturated group having a divalent or higher hydrophobic group with a fatty acid and / or a fatty acid derivative. However, compared to amine ester compounds synthesized from tertiary amines having an unsaturated valence of less than 2, the resulting film is a film of any printing ink of organic solvent-based inks and water-based inks that have opposite liquid properties. As a result, it was found that a polyolefin film excellent in antistatic properties, less bleed whitening with time, and excellent in transparency can be obtained. Is.
That is, the present invention relates to 1 mol of at least one tertiary amine represented by the following general formula (A), 0.8 mol of a fatty acid having 8 to 22 carbon atoms and / or a fatty acid derivative thereof having a linear or branched chain. It is composed of an amine ester compound obtained by reacting ˜1.5 mol, and 10% by weight or more of the amine ester compound is a tertiary amine ester compound in which R ₁ has a divalent or higher unsaturated bond. It is an antistatic agent characterized.

(R ₁ is a linear or branched C 8-22 alkyl group, alkenyl group, hydroxyalkyl group or hydroxyalkenyl group, m and n are integers of 1 or 2, and m + n is 2 Or 3.
The present invention also relates to a polyolefin resin composition characterized by containing 0.1 to 2.0% by weight of such an antistatic agent relative to the polyolefin resin.
Furthermore, the present invention also relates to a polyolefin film comprising the above-mentioned polyolefin resin composition, particularly a polyolefin film in which at least one surface is printed with an organic solvent-based ink and / or a water-based ink.

The antistatic agent of the present invention is suitable for both polyolefin resin compositions containing the same, particularly polyolefin films, and can be used for both organic solvent-based inks and water-based inks that have opposite liquid properties. There is an effect that it is less and can exhibit transparency and excellent antistatic properties.
Although the mechanism of this effect has not been clearly clarified, the improvement in printability, that is, the transfer property of the printing ink to the film surface, is the solvent (including vehicle) in organic solvent-based ink or water-based ink and film. This is presumably due to the interfacial tension between the surfaces and the wettability of the colorant (pigment / dye) contained in the ink. That is, when the antistatic agent of the present invention bleeds out to the film surface, the interface tension between the solvent in the ink and the film surface is greatly reduced due to the unsaturated bond in the structure, and at the same time the wettability of the colorant to the film is improved. By greatly improving, it is presumed that the above-mentioned effect is achieved.

（式中、Ｒ₂及びＲ₃は、直鎖又は分岐鎖を有する炭素数８〜２２の脂肪酸のカルボン酸残基を表す。）
Ｒ₁がヒドロキシアルキル基、ヒドロキシアルケニル基である場合には、反応後に得られる本発明のアミンエステル化合物の中には、Ｒ₁中のヒドロキシ基にエチレンオキサイドが付加した構造の化合物も含まれ得る。 The present invention will be described in detail below.
The amine ester compound of the present invention is one or two of the tertiary amines represented by the above general formula (A), wherein the hydrophobic group contains a tertiary amine having 10% by weight or more of a tertiary amine having a divalent or higher unsaturated bond. A fatty acid and / or fatty acid derivative having 8 to 22 carbon atoms having a straight chain or a branched chain with respect to 1 mol of the species or more is reacted with 0.8 mol to 1.5 mol.
When R ₁ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, the general formula, for example, (A-1), (A-2), (A -3).

(In the formula, R ₂ and R ₃ represent a carboxylic acid residue of a fatty acid having 8 to 22 carbon atoms having a linear or branched chain.)
When R ₁ is a hydroxyalkyl group or a hydroxyalkenyl group, the amine ester compound of the present invention obtained after the reaction may include a compound having a structure in which ethylene oxide is added to the hydroxy group in R _1. .

The amine ester compound of the present invention can be obtained by a known method. For example, a primary amine is charged into a pressure reactor, and ethylene oxide is subjected to addition reaction under a temperature condition of about 150 to 160 ° C. to obtain a tertiary amine. Then, the amine ester compound of this invention is obtained by esterifying a fatty acid and / or a fatty acid derivative with respect to the tertiary amine of general formula (A) obtained in reaction container.

R ₁ in the general formula (A) is a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group or a hydroxyalkenyl group, preferably a linear alkenyl group.
R ₁ has 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. If the number of carbon atoms is less than 8, the film is likely to be blocked. Conversely, if it exceeds 22, bleed whitening may occur over time, and transparency may be impaired.
The amine ester compound according to the present invention contains a tertiary amine ester compound in which R ₁ has a divalent or higher unsaturated bond in an amount of 10% by weight or more, preferably 20.0% by weight or more. contains. There is no upper limit to the proportion of tertiary amine having a divalent or higher unsaturated bond, but if it is less than 10% by weight, the ink transfer property is lowered.
The unsaturated valence of the group R ₁ having an unsaturated bond in the tertiary amine of the general formula (A) is 2 or more, and there is no particular upper limit, but only those having a value of less than 2 (valence 1, saturated bond only) Then, the transfer property of printing ink falls.

Specific examples of the group R ₁ having a divalent or higher unsaturated bond include a linoleoyl group (C18F2; C is carbon number, F is an unsaturated bond valence, the same shall apply hereinafter), α-linolenoyl group (C18F3), and γ-linolenoyl group. (C18F3), α-eleostearoyl group (C18F3), β-eleostearoyl group (C18F3), and arachidonoyl group (C18F4) are exemplified, and linoleoyl group is particularly preferable.

Primary amines as a raw material for the tertiary amine R ₁ is represented by the general formula (A) containing a tertiary amine is a group having a valence of two or more unsaturated bonds, it is obtained by various known methods Can do. However, in consideration of industrial aspects, a method comprising the following steps starting from fats and oils is preferred.
(1) Fat and oil (hydrolysis) → R ₁ -COOH
(2) R ₁ —COOH + NH ₃ → R ₁ —COONH ₄
(3) R ₁ —COONH ₄ (heating) → R ₁ —CONH ₂ + H ₂ O
(4) 2R ₁ -CONH ₂ (catalyst heating) → R ₁ -COONH ₄ + R ₁ -C≡N
(5) R ₁ —C≡N + 2H ₂ → R ₁ —NH ₂ (primary amine)
(6) R ₁ —NH ₂ (EO addition) → General formula (A)
In this case, since the starting material is oil and fat, the unsaturated valence and carbon number of R ₁ in the general formula (A) are different depending on the type of oil and fat. Moreover, the unsaturated valence number and carbon number which comprise fats and oils are generally some mixture.
As fats and oils, almond nut oil, apricot kernel oil, avocado oil, linseed oil, ginger seed oil, ume seed oil, olive oil, orange seed oil, cashew nut oil, pumpkin seed oil, cassava seed oil, walnut nut oil, poppy oil, Wheat germ oil, rice bran oil, sesame oil, rubber kernel oil, goren range seed oil, safflower oil, watermelon seed oil, sudachi seed oil, soybean oil, tea seed oil, evening primrose seed oil, tunbu kernel oil, corn oil, tomato seed oil Specific examples include vegetable oils such as rapeseed oil, palm olein oil, sunflower oil, cottonseed oil and peanut oil, or animal oils such as ducks, chickens and pigs.
Animal oils such as ducks, chickens and pigs can obtain a large amount of primary amines with groups having an unsaturated bond of 2 or more by special distillation, purification, etc. Vegetable oils and fats having abundant divalent or higher unsaturated bonds are preferable, and soybean oil, sunflower oil, rapeseed oil, cottonseed oil, and peanut oil are particularly preferable.

  In the general formula (A), m and n represent the number of moles of ethylene oxide added, and are integers of 1 or 2, and m + n is 2 or 3. When m + n exceeds 3, the film is formed. It becomes easy to block, and if m + n is smaller than 2, the antistatic property is impaired.

In the amine ester compound of the present invention, the fatty acid or fatty acid derivative to be esterified with the above general formula (A) is a fatty acid derivative such as a linear or branched fatty acid having 8 to 22 carbon atoms and a fatty acid methyl ester or ethyl ester. is there.
The number of carbon atoms of the fatty acid and the fatty acid derivative is 8-22, preferably 12-18. If the carbon number is less than 8, the film is likely to block, and conversely if the carbon number exceeds 22, bleed whitening may occur over time, and transparency may be impaired.
Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, isostearic acid, lauric acid methyl ester, and stearic acid ethyl ester, and these may be used alone or in combination of two or more. However, in view of industrial economy, lauric acid and stearic acid are preferable.

  The reaction molar ratio of the fatty acid to be esterified and the fatty acid derivative is from 0.8 mol to 1.5 mol, more preferably from 1.0 mol to 1.2 mol, based on 1 mol of the tertiary amine. If the reaction molar ratio is less than 0.8 mol, smoke generation tends to become intense during film formation. Conversely, if the reaction molar ratio is greater than 1.5 mol, the antistatic property decreases.

  Specific examples of the amine ester compound of the present invention include N, N-dipolyoxyethylene (2) soybean oil alkylamine monolaurate, N, N-dipolyoxyethylene (2) sunflower oil alkylamine monolaurate, N, N-dipolyoxyethylene (2) rapeseed oil alkylamine monostearate, N, N-dipolyoxyethylene (2.5) cottonseed oil alkylamine monostearate, N, N-dipolyoxyethylene (3) peanut Examples thereof include oil alkylamine monostearate, but are not limited thereto.

The antistatic agent of the present invention may contain a known antistatic agent other than the present invention, if necessary, as long as the object of the present invention is not impaired. Known antistatic agents other than the present invention include glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, poly Examples include, but are not limited to, oxyethylene aliphatic alcohol ethers, N, N-diethanolalkylamines, condensates of fatty acids and diethanolamine, and amine ester compounds outside the scope of the present invention.
Specifically, glycerin monostearate, glycerin monooleate, polyglycerin monostearate, polyglycerin monooleate, sorbitan monooleate, sorbitan monoelcate, polyoxyethylene glycerin monooleate, polyoxyethylene sorbitan monooleate, polyethylene glycol Examples include monooleate, polypropylene glycol monooleate, polyoxyethylene oleyl alcohol ether, N, N-diethanollaurylamine, N, N-diethanolstearylamine, and oleic acid diethanolamide. These may be used alone or in combination of two or more.

  The blending amount of the amine ester compound of the present invention with respect to the polyolefin resin or polyolefin film is preferably 0.1% by weight to 2.0% by weight, and more preferably 0.5% by weight to 1.0% by weight. When the blending amount is 0.1% by weight or less, the antistatic property is inferior. On the other hand, if the amount exceeds 2.0% by weight, the antistatic property is not greatly improved, but rather bleed whitening occurs with time, and the transparency is impaired.

  The compounding method of the amine ester compound of the present invention to the polyolefin resin or polyolefin film is performed by a known method. Specifically, a high-concentration master batch may be separately prepared and mixed in an arbitrary process until a film is obtained, or may be mixed in advance with polyolefin powder.

  To the polyolefin film of the present invention, an antioxidant, a lubricant, a colorant, an ultraviolet absorber and various additives and fillers usually used for polyolefin films can be added as additional components within a range that does not impair the object of the present invention. it can.

  The polyolefin of the present invention is not particularly limited, and known ones are used. For example, homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, copolymers of the α-olefins, the α-olefins and the like Copolymers of monomers other than copolymerizable α-olefins and α-olefins, and mixtures thereof. Examples of monomers other than the α-olefin copolymerizable with the α-olefin include vinyl acetate, maleic acid, vinyl alcohol, methacrylic acid, methyl methacrylate, and ethyl methacrylate.

  The polyolefin film of the present invention may be a single layer film or a laminated film in which two or more kinds of resins are laminated.

  As one embodiment of the present invention, there is one in which at least one surface of a polyolefin film is printed with printing ink. Printing on the surface of the polyolefin film can be performed by commonly used methods such as screen printing, flexographic printing, offset printing, and gravure printing.

The composition of the organic solvent-based and water-based ink applied to the film of the present invention includes, for example, a solvent, a colorant, a resin binder, and other additives as required. Examples of the solvent for the organic solvent-based ink include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, and ketone solvents such as methyl ethyl ketone. On the other hand, water-based inks use water as a solvent, and may use alcohols, preferably lower alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, etc., without any particular limitation. Also, common inorganic and organic pigments can be used as colorants for both inks, such as soluble and insoluble organic pigments such as azo, phthalocyanine and naphthol, titanium oxide, calcium carbonate, petals, carbon Inorganic pigments such as black are exemplified.
The resin binder used in the ink may be any styrene-acrylic acid-based, styrene-maleic acid-based acrylic resin, polyurethane resin, rosin-modified resin, or the like that can be produced with a stable ink, alone or It can be used in combination. In addition, waxes, antifoaming agents, dispersing agents and the like may be used as additives. In order to adjust the viscosity of the ink at the time of printing, the above solvent may be used for the organic solvent-based ink, and a diluent using water and alcohols may be used for the water-based ink.
Thus, when the antistatic agent of the present invention is contained in a polyolefin film, the interfacial tension between the solvent in the ink and the film surface as described above is greatly reduced, and at the same time, the wettability of the colorant to the film is greatly improved. . The tendency is that as the valence of the unsaturated bond in the structure of the antistatic agent of the present invention is increased from 2 to 3, and from 1 to 1, and as the ratio of those having a higher valence increases. In addition, the effect is more likely to appear in the case of water-based ink having a larger surface tension than the organic solvent ink.

  When the polyolefin film of the present invention is printed by a known printing machine using the above organic solvent-based ink or water-based ink, the film surface is subjected to a known method such as corona discharge treatment, ozone treatment, plasma treatment, etc. prior to printing. If the surface activation treatment is performed by the above, it is possible to improve the familiarity and adhesion of the ink, and therefore it is desirable to perform the surface activation treatment by some method.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
<1> Analytical Method Before synthesizing the amine ester compound of the present invention, the composition analysis of R ₁ in the general formula (A) of the primary amine derived from fats and oils is specifically performed by gas chromatography (GC). The method was carried out.
Column: 20% DEGS / Uniport B (60-80 mesh, 3 m × 3 m)
Column temperature: 200 ° C, inlet temperature 280 ° C
Detector: FID.
Pretreatment: A primary amine is reacted with formic acid and formaldehyde.
Measurement was performed under the above conditions, and the composition ratio was calculated from the area ratio of the detected peaks. Table 1 shows the composition ratios of primary amines used in Examples and Comparative Examples.
<2> Synthesis of amine ester compounds

Synthesis of amine ester compound A (soybean oil derivative)
A glass autoclave is charged with 1 mol of a primary amine derived from soybean oil, substituted with N ₂ , and further added with 2.0 mol of ethylene oxide at 155 ° C. for 2 hours, and then the obtained compound The amine ester compound A of the present invention was synthesized by reacting 1.0 mol of 0.8 mol of lauric acid and introducing N ₂ gas while raising the temperature to 160 ° C. for 4 hours. The obtained amine ester compound A is used for the test described later.

Synthesis of Amine Ester Compounds B to E and Comparative Amine Ester Compounds A ′ and B ′ As shown in Table 2, the synthesis of amine ester compounds B to E and Comparative Amine Ester Compounds A ′ and B ′ are shown in Table 2. It carried out by. The obtained amine ester compounds B to E and comparative amine ester compounds A ′ and B ′ are also subjected to the test described later.

  The symbols in Table 2 have the following meanings. “C12 = 98” in the column of the carbon number composition (%) of the reacted fatty acid and fatty acid derivative means 98% of lauric acid; “C18 * = 98” contains 98% of stearic acid methyl ester. “C16 / C18 = 35/65” means containing 35% palmitic acid and 65% stearic acid; “C18 = 98” means containing 98% stearic acid.

＜３＞本発明以外の帯電防止剤の合成

<3> Synthesis of antistatic agents other than the present invention

Synthesis of antistatic agent (1) other than the present invention In a glass autoclave, 1 mol of primary amine derived from soybean oil and fats was charged, N ₂ substitution was performed, and 2.0 mol of ethylene oxide was added at 155 ° C. for 2 hours. And an antistatic agent (1) other than the present invention was synthesized. The obtained antistatic agent (1) is subjected to the test described below.

Synthesis of antistatic agent other than the present invention (2) In a glass autoclave, 1 mol of glycerin and 1.3 mol of industrial stearic acid were charged, and N ₂ gas was introduced, and at the same time the temperature was raised to 200 ° C. under a basic catalyst. Then, esterification was performed for 5 hours to obtain glycerin stearic acid ester. The obtained glycerin stearate was removed from the diester by molecular distillation to synthesize an antistatic agent (2) other than the present invention which is a glycerin monostearate having a monoester content of 95%, which will be described later. Used for testing.
<4> Mixing ratio of antistatic agent

The amine ester compound of the present invention and the antistatic agent (1) or (2) other than the present invention are blended as shown in Table 3, and the antistatic agents of Examples 1 to 6 and the antistatic agents of Comparative Examples 1 to 3 are used. Obtained. The obtained antistatic agents of Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to the tests described below.
<5> Preparation of evaluation film

The antistatic agent of Examples 1-6 and the antistatic agent of Comparative Examples 1-3 are mix | blended with the content of Table 3 to crystalline polypropylene with a melt flow rate of 3.0 g / 10 min and a crystallinity of 97%. As an antiblocking agent, 0.1% by weight of silica having a particle size of 2.0 μm was added and dissolved and mixed. This resin was extruded from a T-die, and a stretched film having a thickness of 20 μm was obtained using a tenter biaxial stretching machine. The surface was subjected to corona discharge treatment according to a conventional method so that the Nule index was 40 mN / m. The evaluation results of the obtained film are shown in Table 3.
<6> Evaluation method

The film was evaluated by the following method.
(1) Bleed whitening and transparency evaluation A test piece was cut out from a film subjected to corona discharge treatment and allowed to stand for 14 days under a constant temperature and humidity condition at a temperature of 23 ° C. and a relative humidity of 50%, and then a HAZE measuring device (TC-HIIIDPK: TEPCO). The HAZE value was measured with “Color”. The smaller the value, the better the transparency. HAZE (%) was evaluated according to the following criteria.
2% or less ◎ ◎ (excellent)
2%-3% ... ○ (good)
3% to 5% ... △ (possible)
5% or more ・ ・ ・ × (defect)

(2) Antistatic properties (surface resistivity)
A predetermined test piece is prepared from the corona discharge-treated film before printing, and the surface specific resistance value of the corona discharge-treated surface of the test piece according to JIS-K-6911 (super insulation meter P-616: manufactured by Kawaguchi Electric Co., Ltd.) Was measured. The smaller the value, the better the antistatic property. The surface resistivity (Ω) was evaluated according to the following criteria.
11 or less ◎ ◎ (excellent)
11-12 ... ○ (good)
12-13 ... △ (possible)
13 or more ・ ・ ・ × (defect)

(3) Printability evaluation (ink transfer property)
Using a gravure printer on the corona discharge treated surface of the film, an organic solvent-based ink and a water-based ink were printed to evaluate the ink transfer property with the film surface.
In the transferability evaluation, the printed surface was observed with an optical microscope, and the transfer amount of repelling ink was evaluated according to the following criteria.
◎: No repelling is observed, and the amount of ink transferred is large. ○: Almost no repelling is observed, and the amount of transferred ink is somewhat large. △: Some repelling is observed, and the amount of ink transferred is normal. , Ink transfer amount is small XX: Too much repellency and less ink transfer amount Toyo Ink Mfg. Co., Ltd.'s “LP Super” is used as an organic solvent-based ink. Diluted to ˜30% by weight was used.
As the water-based ink, “Aqua Ecole” manufactured by Toyo Ink Mfg. Co., Ltd. was used to dilute it to a solid concentration of 20 to 30% by weight and an alcohol concentration of 30% or less using a dedicated diluent solvent.

As shown in Table 3, the polyolefin films containing the amine ester compounds of the present invention of Examples 1 to 6 have improved ink transferability in both organic solvent-based inks and water-based inks having opposite liquid properties, and Excellent antistatic properties, less bleed whitening over time, and excellent performance in transparency.

Claims (7)

One mole of at least one tertiary amine represented by the following general formula (A) is a straight chain or branched chain fatty acid having 8 to 22 carbon atoms and / or a fatty acid derivative thereof of 0.8 mole to 1.5 mole. consists amine ester compound obtained by reacting, 10% or more by weight of the amine ester compound, characterized in that R ₁ is an ester compound of a tertiary amine having a divalent or more unsaturated bonds, charge Inhibitor.

(R ₁ is a linear or branched C 8-22 alkyl group, alkenyl group, hydroxyalkyl group or hydroxyalkenyl group, m and n are integers of 1 or 2, and m + n is 2 Or 3. The antistatic agent according to claim 1, wherein 20% by weight or more of the amine ester compound is a tertiary amine ester compound in which R ₁ in the general formula (A) has a divalent or higher unsaturated bond. .   The antistatic agent according to claim 1 or 2, wherein the tertiary amine represented by the general formula (A) is derived from a vegetable oil.   The antistatic agent according to claim 3, wherein the vegetable oil is one or more selected from the group consisting of soybean oil, sunflower oil, rapeseed oil, cottonseed oil and peanut oil.   A polyolefin resin composition comprising the antistatic agent according to any one of claims 1 to 4 in an amount of 0.1 to 2.0% by weight based on the polyolefin resin.   A polyolefin film comprising the polyolefin resin composition according to claim 5. A polyolefin film comprising the polyolefin resin composition according to claim 5, wherein at least one surface thereof is printed with an organic solvent-based ink and / or a water-based ink.