JP2010106241A - Antistatic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic film excellent in heat-sealing properties, etc., without impairing primary surface characteristics of a base resin making up of an antistatic film. <P>SOLUTION: The antistatic film includes (A) 40-98 wt.% of a polyolefin resin, (B) 1-30 wt.% of an antistatic agent including a block polymer having a structure formed by repeatedly and alternately bonding a block of polyolefin (a) to a block of a hydrophilic polymer (b) having a volume resistivity value of 1×10<SP>5</SP>to 1×10<SP>11</SP>Ω×cm and (C) 1-30 wt.% of carbodiimide compound based on the total weight of (A) to (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic film, and more particularly to an antistatic film excellent in heat sealability.

Conventionally, a block polymer having a structure in which a polyolefin block and a hydrophilic polymer block having a volume specific resistance value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are repeatedly bonded alternately and a base resin polyolefin resin A multilayer film composed of a surface film composed of an antistatic resin composition as an essential component and a base film composed of a thermoplastic resin has been proposed as having excellent antistatic properties and strength (see, for example, Patent Document 1). .

JP 2002-321314 A

However, since the above-mentioned multilayer film contains a block polymer in the surface layer film, it has a considerable influence on the film surface characteristics of the polyolefin resin, which is the base resin, and heat sealability deteriorates, and surface roughness and surface precipitates are present. There is a problem that painting and printing are difficult.
An object of the present invention is to provide an antistatic film excellent in heat sealability and the like without impairing the original surface characteristics of the base resin constituting the antistatic film (there is surface roughness and surface deposits). is there.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, this invention contains the following (A)-(C), and based on the total weight of (A)-(C), (A) is 40-98%, (B) is 1-30. %, (C) 1-30% antistatic film (A) polyolefin resin (B) polyolefin (a) block, volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω
・ Antistatic agent (C) carbodiimide compound consisting of a block polymer having a structure in which blocks of hydrophilic polymer (b) of cm are repeatedly and alternately bonded; and the film is coated and / or printed It is a film article.

The antistatic film of the present invention has the following effects.
(1) Excellent permanent antistatic property and heat sealability.
(2) The original surface characteristics of the base resin constituting the antistatic film are not impaired.

[Polyolefin resin (A)]
Examples of the polyolefin resin (A) in the present invention include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and Copolymer (random and / or block addition) with one or more ethylene and other α-olefin [carbon number (hereinafter abbreviated as C) 4-12] [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate copolymer (EVA
) [Copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [Copolymerization ratio (weight ratio) = 95 / 5-60 / 40].
Among these, polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or ethylene and C4-12 α- are preferable from the viewpoints of compatibility with (B) and (C) described later and heat sealability. Copolymers with one or more olefins [copolymerization ratio (weight ratio) = 90/10 to 10/90, random and / or block addition], ethylene / vinyl acetate copolymer (EVA) [copolymerization ratio ( Weight ratio) = 85/15 to 60/40].

The melt flow index (hereinafter abbreviated as MFR) of (A) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of antistatic properties and mechanical properties of the film described later. MFR conforms to JIS K6758 (for example, in the case of polypropylene: 23
0 ° C., load 2.16 kgf, polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (A) is preferably 98% or less, more preferably 0 to 80%, particularly preferably 0 to 70% from the viewpoint of antistatic properties. The crystallinity is measured by a method such as X-ray diffraction, infrared absorption spectrum, etc. [Refer to “Solid Structure of Polymers—Human Laboratory for Polymer Experiments 2” (Hatsugoro Nanshino), page 42, published by Kyoritsu Shuppan 1958).

[Antistatic agent (B)]
As the block polymer (BP) constituting (B), the block polymer described in International Publication WO00 / 47652 can be used.
As the polyolefin (a) constituting (BP), a carbonyl group-containing group (carboxyl group, aldehyde group, carboxyalkyl group, amide group is included, and a carboxyl group is preferable from the viewpoint of easy formation of a block polymer. ) At both ends of the polymer, polyolefin (a2) having hydroxyl groups at both ends of the polymer, polyolefin (a3) having amino groups at both ends of the polymer, and a carbonyl group-containing group. A polyolefin (a4) having one end of the polymer, a polyolefin (a5) having a hydroxyl group at one end of the polymer, and a polyolefin (a6) having an amino group at one end of the polymer can be used. Among these, polyolefins (a1) and (a4) having a carbonyl group-containing group are preferable because of easy modification.

As (a1) to (a3), those in which a carbonyl group-containing group, a hydroxyl group, and an amino group are introduced at both ends of a polyolefin that can be modified at both ends are used.
As (a4) to (a6), those obtained by introducing a carbonyl group-containing group, a hydroxyl group, and an amino group into one end of a polyolefin that can be modified at least one end are used.
The polyolefin having a terminal-modifiable polyolefin includes a functional group (double bond, amino group, carboxyl group, allyl group, glycidyl group, etc., which can be modified at the end of the polyolefin chain. Is preferred).

  Examples of the modifiable polyolefin include a polyolefin (a0) whose main component (preferably the content is 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80 to 100% by weight). Can be used. (A0) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a modifiable end group, and when (a0) is modified, a functional group (carbonyl group) A mixture of a polyolefin having a containing group, a hydroxyl group or an amino group) introduced at both ends, a polyolefin having a functional group introduced at one end, and a polyolefin having no functional group introduced.

  As (a0), a polyolefin [polymerization method] obtained by (co) polymerization (meaning polymerization or copolymerization) of one or a mixture of two or more C2-30 olefins, and a high molecular weight A low molecular weight polyolefin [thermal degradation method] obtained by a thermal degradation method of polyolefin (polyolefin obtained by polymerization of C2-30 olefin) can be used.

C2-30 olefins include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10 from the viewpoint of antistatic properties), and C4-30 (antistatic properties). To preferably 4-18, more preferably 4-8).
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, 1,4- Examples include pentadiene, 1,6-hexadiene, cyclopentadiene, and 1,11-dodecadiene.
Among these, C2-12 olefins (ethylene, propylene, C4-12 α-olefins, butadiene and / or isoprene, etc.) are preferable from the viewpoint of antistatic properties, and C2-10 (ethylene, propylene, C4-10 α-olefin and / or butadiene, etc.), particularly preferred are ethylene, propylene and / or butadiene.

The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained by, for example, the method described in JP-A-3-62804.
The polyolefin obtained by the polymerization method can be produced by various methods, for example, easily obtained by (co) polymerizing the olefin in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst, a Ziegler-Natta catalyst, or the like. be able to.
As a radical catalyst, for example, di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-dicarbonate ester, azo compound, etc., and molybdenum oxide are attached to a γ-alumina support. And the like. Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. Examples of Ziegler catalysts and Ziegler-Natta catalysts include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .
Examples of the polymerization method include a method in which a catalyst and a monomer are added to a hydrocarbon solvent such as xylene and toluene cooled to −50 to −100 ° C. for polymerization.
From the viewpoint of easy introduction of a carbonyl group-containing group which is a modifying group and easy availability, a low molecular weight polyolefin by a thermal degradation method is preferred.

Mn of (a0) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000 from the viewpoint of antistatic properties.
The amount of the double bond in (a0) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per 1,000 C from the viewpoint of antistatic properties.
The average number of double bonds per molecule is preferably 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.5 from the viewpoints of repetitive structure formation and antistatic properties. ~ 2.5, most preferably 1.8-2.2.
In the thermal degradation method, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 with an Mn in the range of 800 to 6,000 can be easily obtained [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

As the polyolefin (a1) having a carbonyl group-containing group at both ends of the polymer, both ends of the polyolefin which can be modified at both ends are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid). , Its C1-4 alkyl ester or its anhydride.
The same applies hereinafter. The polyolefin (a11) having a structure modified with), the polyolefin (a12) having a structure obtained by secondary modification of (a11) with a lactam or an aminocarboxylic acid, and a structure obtained by oxidizing or hydroformylating a polyolefin capable of modifying both ends. Polyolefin (a13), polyolefin (a14) having a structure in which (a13) is secondarily modified with lactam or aminocarboxylic acid, polyolefin (a15) having a structure in which (a13) is secondarily modified with hydroxyamine, and these 2 Mixture of more than seeds, etc .; polyolefin (a2) having hydroxyl groups at both ends of the polymer has polyolefin (a21) having a structure in which (a11) is modified with hydroxylamine, and has a structure in which (13) is modified with hydroxylamine Polyolefin (a 2), and a mixture of two or more of these; as the polyolefin (a3) having amino groups at both ends of the polymer, polyolefins (a31) and (a12) having a structure in which (a11) is secondarily modified with diamine A polyolefin (a32) having a structure secondary modified with diamine, a polyolefin (a33) having a structure modified with hydroxyamine (a12), a polyolefin (a34) having a structure secondary modified with diamine (a13), Examples include polyolefin (a235) having a structure in which (a13) is modified with hydroxyamine, polyolefin (a36) having a structure in which (a214) is secondarily modified with diamine, and a mixture of two or more thereof.

(A11) can be obtained by modifying a polyolefin capable of modifying both ends with an α, β-unsaturated carboxylic acid (anhydride).
Examples of α, β-unsaturated carboxylic acids (anhydrides) include C3-12 carboxylic acids such as monocarboxylic acids [(meth) acrylic acid, etc.], dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. ), These alkyl (C1-4) esters [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.], and anhydrides thereof.
Of these, dicarboxylic acids, their alkyl esters and their anhydrides are preferred, and maleic acid (anhydride) and fumaric acid are particularly preferred from the viewpoint of reactivity with polyolefins capable of modifying both ends. Is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) to be used is preferably 0.5 to 40% based on the weight of the polyolefin that can be modified at both ends, from the viewpoint of the formation of a repeating structure and antistatic properties. %, More preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight.
The modification of the polyolefin capable of modifying both ends with an α, β-unsaturated carboxylic acid (anhydride) can be carried out in various ways, for example, by either the solution method or the melting method to the terminal double bond of the polyolefin capable of modifying both ends. This method can be carried out by thermally adding (ene reaction) an α, β-unsaturated carboxylic acid (anhydride).
As a solution method, an α, β-unsaturated carboxylic acid (anhydride) is added to a polyolefin that can be modified at both ends in the presence of a hydrocarbon solvent such as xylene and toluene, and the reaction is performed in an inert gas atmosphere such as nitrogen. The method of making it react at -230 degreeC etc. are mentioned.
As a melting method, there is a method in which a polyolefin capable of modifying both ends is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. Can be mentioned.
Among these methods, the solution method is preferable from the viewpoint of the uniformity of the reaction.

(A12) can be obtained by secondary modification of (a11) with lactam or aminocarboxylic acid.
As the lactam or aminocarboxylic acid, those described above can be used.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred from the viewpoint of reactivity of secondary modification, and caprolactam is more preferred. Laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used is preferably from the viewpoint of antistatic properties, and preferably 0.1 to 20 lactams or aminocarboxylic acids per residue obtained by removing the carboxyl group from the α, β-unsaturated carboxylic acid. More preferably, the number is 0.3 to 15, particularly preferably 0.5 to 10.

(A13) can be obtained by introducing a carbonyl group-containing group by oxidizing a polyolefin capable of modifying both ends with oxygen and / or ozone or hydroformylating by an oxo method.
The introduction of the carbonyl group-containing group by oxidation can be performed by various methods, for example, the method described in US Pat. No. 3,692,877. Introduction of carbonyl group-containing groups by hydroformylation can be accomplished by various methods, for example, Macromolecules, Vol. 31, 5943 page.

(A14) can be obtained by secondary modification of (a13) with lactam or aminocarboxylic acid.
As lactam and aminocarboxylic acid, what was mentioned above is mentioned, The usage-amount is also the same.

  (A15) can be obtained by secondary modification of (a13) with hydroxylamine. Hydroxylamine includes C2-10 hydroxylamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3- Examples include aminomethyl-3,5,5-trimethylcyclohexanol. Of these, 2-aminoethanol is preferred. The modification with hydroxylamine can be carried out by directly reacting (a11) with hydroxylamine. The reaction temperature is usually 120 to 230 ° C. The amount of hydroxyl group of hydroxylamine used for modification is 0.1 to 2, preferably 0.3 to 1.5, per residue of α, β unsaturated carboxylic acid (anhydride) in (a11). The number is preferably 0.5 to 1.2, and most preferably 1.

  (A3) can be obtained by secondary modification of (a11) with diamine. Examples of the diamine include C2-18, preferably 2-12 diamines such as ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine and the like. Of these, ethylenediamine is preferred. Modification with diamine can be carried out by directly reacting (a11) with diamine. The reaction temperature is usually 120 to 230 ° C. The amount of the amino group of the diamine used for modification is 0.1 to 2, preferably 0.3 to 1.5, per residue of α, β unsaturated carboxylic acid (anhydride) in (a11). The number is particularly preferably 0.5 to 1.2, and most preferably 1.

(A32) can be obtained by secondary modification of (a12) with hydroxylamine.
Examples of hydroxylamine include those exemplified in (a15), and the amount used thereof is also the same.

(A32) can be obtained by secondary modification of (a13) with diamine.
Examples of the diamine include those exemplified above, and the amount used is also the same.

  The polyolefins (a4) to (a6) whose one end is modified can be obtained by modifying a polyolefin whose one end can be modified by the same method as (a1) to (a3).

Mn of the polyolefin (a) is preferably from 800 to 25,000, more preferably from 1,000 to 20,000, and particularly preferably from 2,500 to 5,000 from the viewpoint of heat resistance and reactivity with (b) described later. 10,000.
Moreover, it is preferable that (a) contains a carboxyl group, in which case the acid value of (a) (mgKOH / g, the following is indicated only by numerical values) is from the viewpoint of reactivity with (b). Preferably, it is 4-280, More preferably, it is 4-100, Most preferably, it is 5-50. In the case of containing a hydroxyl group, the hydroxyl value of (a) (mgKOH / g, the following is shown only by numerical values) is preferably 4 to 280, more preferably 4 to 100, from the viewpoint of reactivity with (b). Especially preferably, it is 5-50. In the case of containing an amino group, the amine value of (a) (mgKOH / g, the following is shown only by numerical values) is preferably from 4 to 280, more preferably from 4 to 280 from the viewpoint of reactivity with (b). 100, particularly preferably 5-50.

The hydrophilic polymer (b) constituting the block polymer (BP) is 1 × 10 ⁵ to 1 × 10 ¹¹ (preferably 1 × 10 ⁶ to 1 × 10 ¹⁰ , more preferably 1 × 10 ⁷ to 1 × 10 ^9. ) It has a volume resistivity value of Ω · cm. When the volume resistivity is less than 1 × 10 ⁵ , the mechanical properties of the film are deteriorated, and when it exceeds 1 × 10 ¹¹ , the antistatic property of the film is lowered. The volume specific resistance value is a value measured by an after-mentioned method in an atmosphere of 23 ° C. and 50% RH.
Here, the hydrophilic property means a hygroscopic property, and the hydrophilic polymer means a polymer having a volume specific resistance value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm.

As the hydrophilic polymer (b), polyether (b1), polyether-containing hydrophilic polymer (b2), cationic polymer (b3) and anionic polymer (b4) can be used.
As (b1), polyether diol (b1-1), polyether diamine (b1-2), and modified products thereof (b1-3) can be used. (B2) includes polyether ester amide (b2-1) having a segment of polyether diol (b1-1) as a polyether segment forming component, and polyether amide imide (b2-) having a segment of (b1-1). 2), polyether ester (b2-3) having a segment of (b1-1); polyether amide (b2-4) having a segment of (b1-2), and (b1-1) or (b1-2) ) Polyether urethane (b2-5) having a segment can be used.
As (b3), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule can be used.
As (b4), the dicarboxylic acid (e1) having a sulfo group and the diol (b01) or the polyether (b1) are essential structural units, and 2 to 80, preferably 3 to 60 in the molecule. An anionic polymer having a sulfo group can be used.

Of the polyether (b1), the polyether diol (b1-1) is an alkylene oxide (hereinafter abbreviated as AO) containing ethylene oxide (hereinafter abbreviated as EO) as an essential component in the diol (b01) or dihydric phenol (b02). ) Those having a structure obtained by addition reaction of (C2-12), for example, those represented by the following general formula.

H (OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} H

In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from (b01) or (b02), A ¹ is a C2-4 alkylene group; m and m ′ are 1-300, preferably 2-250, more preferably Represents an integer of 10 to 100, and m and m ′ may be the same or different. Further, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form when these are composed of two or more oxyalkylene groups is random. And / or blocks.

Examples of the diol (b01) include C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohols (eg, aliphatic, alicyclic and araliphatic dihydric alcohols) and C1-12. A tertiary amino group-containing diol may be mentioned.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol (hereinafter, EG, PG, 1,4-BD, 1,6-HD, respectively). And abbreviated as NPG) and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

As the tertiary amino group-containing diol, aliphatic or alicyclic primary monoamine (C1-12, preferably 2-10, more preferably 2-8) bishydroxyalkyl (alkyl group C1-12, preferably 2-10, more preferably 2-8) and aromatic (aliphatic) primary monoamines (C6-12) bishydroxyalkyl (alkyl group C1-12) compounds.
Monoamine bishydroxyalkylates are obtained by reacting, for example, monoamines with C2-4 AO [eg EO, PO and butylene oxide], or monoamines with C1-12 halogenated hydroxyalkyl (eg 2-bromoethyl alcohol and 3 It can be easily obtained by reacting with (chloropropyl alcohol).

Examples of aliphatic primary monoamines include methylamine, ethylamine, 1- and 2-propylamine, n- and i-amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2- and 3 -Aminoheptane, heptylamine, nonylamine, decylamine, undecylamine and dodecylamine.
Examples of the alicyclic primary monoamine include cyclopropylamine, cyclopentylamine, and cyclohexylamine.
Examples of the aromatic (aliphatic) primary monoamine include aniline and benzylamine.

  Examples of the dihydric phenol (b02) include C6-18 (preferably 8-18, more preferably 10-15), such as monocyclic dihydric phenol (for example, hydroquinone, catechol, resorcin and urushiol), bisphenol (for example, bisphenol A). And -F) and condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

  Of (b01) and (b02), from the viewpoint of antistatic properties, dihydric alcohol and dihydric phenol are preferred, aliphatic dihydric alcohol and bisphenol are more preferred, and EG and bisphenol A are particularly preferred.

As AO to be subjected to addition reaction with diol (b01) or dihydric phenol (b02), for example, C3-12 AO (for example, PO, 1,2-, 1,4-, 2,3- and 1, other than EO) 3-butylene oxide and a mixture of two or more thereof), but other AO and substituted AO may be used in combination if necessary.
Examples of other AO and substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (for example, epichlorohydrin and epibromohydrin). The amount of each other AO and substituted AO used is the total AO
From the viewpoint of antistatic properties, it is preferably 30% or less, more preferably 0 or 25%, and particularly preferably 0 or 20% or less based on the weight.

  The number of added moles of AO is preferably 1 to 300 moles, more preferably 2 to 250 moles per hydroxyl group of (b01) or (b02), from the viewpoint of the volume resistivity value of the hydrophilic polymer (b). Preferably it is 10-100 mol. When two or more kinds of AO are used in combination, the coupling form may be random and / or block.

The addition reaction of AO can be performed, for example, in the presence of an alkali catalyst (for example, potassium hydroxide and sodium hydroxide) at 100 to 200 ° C. and a pressure of 0 to 0.5 MPaG.
The content of oxyalkylene units in the polyether diol (b1-1) is based on the weight specific value of the hydrophilic polymer (b) and the dispersibility of (B) in (A) based on the weight of (b1-1). From this viewpoint, it is preferably 5 to 99.8%, more preferably 8 to 99.6%, and particularly preferably 10 to 98%. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 from the viewpoint of the volume resistivity value of (b) and the dispersibility of (B) in (A) based on the weight of the polyoxyalkylene chain. -100%, more preferably 10-100%, particularly preferably 50-100%, most preferably 60-100%.

The polyether diamine (b1-2) has a structure in which the hydroxyl group of the polyether diol (b1-1) is modified to an amino group (primary or secondary amino group), for example, a general formula: RNH-A ² — Examples include (OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} —A ² —NHR. Accordingly, the content of the oxyethylene unit in the polyoxyalkylene chain is the same as in the case of (b1-1), and the content of the oxyalkylene unit in (b1-2) is the same as that of the corresponding oxyalkylene in (b1-1). Same as unit content.
Symbols E ¹ , A ¹ , m and m ′ in the above formula are the same as described above, A ² represents a C2-4 alkylene group, and A ¹ and A ² may be the same or different. R represents H or a C1-4 (preferably 1 or 2) alkyl group.
(B1-2) can be easily obtained by changing both terminal hydroxyl groups of (b1-1) to amino groups by various methods.
As a method of changing a hydroxyl group to an amino group, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b1-1) to form an amino group [for example, (b1-1) and acrylonitrile are combined. A method of reacting and hydrogenating the resulting cyanoethylated product], a method of reacting (b1-1) with an aminocarboxylic acid or lactam, and a method of reacting (b1-1) with a halogenated amine under alkaline conditions. Can be mentioned.

  Examples of the modified product (b1-3) of (b1-1) or (b1-2) include, for example, an aminocarboxylic acid modified product (terminal amino group) of (b1-1) or (b1-2), and an isocyanate modified product thereof. (Terminal isocyanate group) and the same epoxy modified product (terminal epoxy group).

  Mn of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, and particularly preferably 1,000 to 15 from the viewpoint of heat resistance and reactivity with the block of the polyolefin (a). 1,000, most preferably 1,200 to 8,000.

  Examples of the polyether-containing hydrophilic polymer (b2) include the polyether-containing hydrophilic polymer (b2) described in International Publication WO00 / 47652.

The cationic polymer (b3) has 2 to 80, preferably 3 to 60, cationic groups (c2) in the molecule separated by a nonionic molecular chain (c1).
Examples of (c2) include groups having a quaternary ammonium salt and a phosphonium salt.

As the counter anion of (c2), Hammett acidity function (-H ₀₎ super strong acid anions 12-20, and other anions. Examples of super strong acids include (1) super strong acids (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of protonic acid (d1) and Lewis acid (d2), and (2) protonic acid (peroxygen). Chloric acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, etc.).
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , and ClO ₄ ^−. It is done.

Specific examples of (d1) include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. Specific examples of (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.
The combination of (d1) and (d2) is arbitrary, but preferred examples of superacid anions derived from these combinations include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , TaF ₆ ^−. , BF ₃ Cl ⁻ , PF ₅ Cl ⁻ , SbF ₅ Cl ⁻ , AsF ₅ Cl ⁻ , TaF ₅ Cl ⁻ , BF ₃ Br ⁻ , PF ₅ Br ⁻ , SbF ₅ Br ⁻ , AsF ₅ Br ⁻ , TaF ₅ Br ⁻ BF ₃ I ⁻ , PF ₅ I ⁻ , SbF ₅ I ⁻ , AsF ₅ I ^−, TaF ₅ I ^{− and the} like, and a combination of two or more of these may be used. Among these counter anions, from the viewpoint of heat resistance, an anion of a super strong acid is preferable, BF ₄ ⁻ , PF ₆ ⁻ , BF ₃ Cl ⁻ and PF ₅ Cl ⁻ are particularly preferable, and BF ₄ ⁻ and are particularly preferable. PF ₆ ⁻ .

  The nonionic molecular chain (c1) includes a divalent hydrocarbon group, or an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond, and / or Or at least one divalent organic group selected from the group consisting of a hydrocarbon group having a siloxy bond and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; and combinations of two or more thereof. It is done.

  Examples of the divalent hydrocarbon group include a C1-18 (preferably 2-8) linear or branched aliphatic hydrocarbon group (an alkylene group, an alkenylene group, etc.) such as ethylene, propylene, tetramethylene, hexamethylene, Decamethylene, dodecamethylene, 2,2,4-trimethylhexamethylene, etc .; C6-20 aromatic hydrocarbon groups such as 1,3- and 1,4-phenylene, 2,4- and 2,6-tolylene, 4 , 4′- and 2,4′-methylenebisphenylene, m- and p-xylylene, α, α, α ′, α′-tetramethylxylylene, naphthylene, etc .; C4-15 alicyclic hydrocarbon group, Examples include cyclohexylene, methylcyclohexylene, 4,4′-methylenebiscyclohexylene, 2,5- and / or 2,6-norbornylene. That.

The divalent hydrocarbon group having an ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and / or siloxy bond includes (poly) oxyalkylene A group such as a residue of the polyether diol (b-1) [eg-(OA ¹ ) _m -E ^1- (A ¹ O) _{m '} -(where E ¹ , A ¹ , m and m' are The same as above), and the residue of a monoether diol represented by the general formula -A ¹ -O-E ^1- (wherein E ¹ and A ¹ are the same as above); Residues of polythioethers (replaced by sulfur atoms); Residues of polyesters and / or polyamides, eg groups of the following general formulas (1) to (4); Residues of polyurethanes and / or polyureas For example, a group represented by the following general formula (5); a residue of polycarbonate [derived from the diol (b01) and phosgene]; a residue of polysiloxane (polyorganosiloxane such as polydimethylsiloxane) .

In the general formulas (1) to (5), D is an oxygen atom or imino group, R ¹ is a C 1-11 hydrocarbon group, R ² is a divalent organic group bonded to a cationic group, and E ² is a diol. Residue (when D is an oxygen atom) or diamine residue (when D is an imino group), E ³ is a residue of a dicarboxylic acid,
E ⁴ is a diisocyanate residue described later, u and v are 0 or 1, and k is an integer of 1-20.
R ¹ includes a lactam residue (when D is an imino group) and a lactone residue (when D is an oxygen atom), the lactam as described above, and the lactone as a lactone corresponding to the lactam. (Such as caprolactone). R ² includes a C 2-12 divalent hydrocarbon group such as an alkylene group, and the (poly) oxyalkylene group [—A ¹ —
^{O-E 1 -, - (} A 1 O) m -E 1 - (OA 1) m '-] and the like.

Among E ² , the diol residue may be a dihydric alcohol (for example, C2-12 as described above).
Aliphatic, alicyclic and aromatic dihydric alcohols), these AO (C2-4) adducts (additional moles of 1-20 or more), dihydric phenols (for example, C6-18 as described above) Examples thereof include residues obtained by removing hydroxyl groups from diols, such as AO (C2-4) adducts of dihydric phenol) (additional moles of 2 to 20 or more), and mixtures of two or more thereof.

Among E ² , the diamine residue may be a low molecular weight diamine such as a diamine corresponding to the diisocyanate: C2-20 aliphatic diamine (ethylenediamine, propylenediamine, hexamethylenediamine, 1,12-dodecanediamine, etc.), C6 -15 alicyclic diamine (1,4-cyclohexylenediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane, etc.), C8-15 araliphatic diamine (xylylenediamine, etc.), C6-15 fragrance Group diamines [p-phenylenediamine, 2,4- and 2,6-toluenediamine, 2,2-bis (4,4′-diaminophenyl) propane, etc.], the polyether diamine (b1-2), and these And a residue obtained by removing an amino group from a diamine, such as a mixture of two or more thereof.

E ³ may be a dicarboxylic acid [C4-12 aliphatic dicarboxylic acid (for example, succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.) Dicarboxylic acid), C8-15 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, etc.), and residues obtained by removing the carboxyl group from dicarboxylic acid such as a mixture of two or more thereof.
Examples of E ⁴ include residues obtained by removing isocyanate groups from diisocyanates (for example, aromatic, aliphatic, alicyclic and araliphatic diisocyanates, modified products thereof, and mixtures of two or more thereof).

Examples of the diisocyanate include C (excluding carbon in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to 18 aliphatic diisocyanate, C4 to 15 alicyclic diisocyanate, and C8 to 15 aromatic fat. Group diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof.
Specific examples of the aromatic diisocyanate include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and 4,4. '-Diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanato Examples thereof include diphenylmethane and 1,5-naphthylene diisocyanate.
Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified diisocyanate include urethane-modified products, urea-modified products, carbodiimide-modified products, and uretdione-modified products.
Of these, TDI, MDI and HDI are preferred, and HDI is particularly preferred.

  The molecular weight of the nonionic molecular chain (c1) is usually a molecular weight of 28 or more and Mn 10,000 or less, preferably Mn 300 to 5,000. Of these nonionic molecular chains (c1), a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable, and a C1-8 alkylene group (such as a hexamethylene group) is more preferable. , Phenylene groups; and (poly) oxyalkylene groups, particularly preferred are (poly) oxyethylene groups and (poly) oxypropylene groups.

  Examples of the cationic polymer (b3) include those having a repeating unit represented by the following general formula (6).

In the formula, M is a nitrogen atom or phosphorus atom, J ⁻ is a counter anion, d is an integer of 2 to 60, L ¹ is a nonionic molecular chain (c1), R ³ and R ⁴ are monovalent nonionic organic compounds It is a group. Further, (b3) is a divalent nonionic organic compound in which adjacent R ³ and / or R ⁴ in the general formula (6) are bonded to each other as shown by the following general formula (7) or (8). It may become a group (L ³ , L ⁵ ) and may form a ring together with M ⁺ .

In the formula, M is a nitrogen atom or phosphorus atom, L ² , L ³ , L ⁴ and L ⁵ are divalent nonionic molecular chains, R ⁴ and R ^{4 ′} are monovalent nonionic organic groups, J ⁻ Is a counter anion, and e is an integer of 1-30.

R ³ , R ⁴ and R ^{4 ′ in the} general formulas (6) and (7) may have an ether bond or an ester bond, and may be an aliphatic, cycloaliphatic or aromatic group of C1-20. Monovalent hydrocarbon group [eg, alkyl group (methyl group, ethyl group, octyl group, dodecyl group, etc.), alkenyl group (allyl group, 1-butenyl group, oleyl group, etc.), (substituted) aralkyl group (benzyl group, 4-methylbenzyl group, etc.), alicyclic hydrocarbon group (cyclohexyl group, etc.), alkoxy (C1-12) alkyl (C1-20) group (methoxyethyl group, etc.), acyloxy (C1-12) alkyl (C1- 20) group (acetoxy group and the like)] and the like.
d is an integer of usually 2 to 60 or more, preferably 3 to 50, more preferably an integer of 5 to 30 from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (a1) to (a6). is there.

Examples of L ^{1 to} L ⁵ include the nonionic molecular chain (c1) as described above.

Preferable examples of the cationic polymer (b3) are those having a repeating unit of the general formula (6) or (8). As a more preferable example, in the general formula (6), R ³
, R ⁴ is a C1-8 alkyl group, L ¹ is a polyester residue [particular preference is given to a polyester in which R ² is a C2-4 alkylene group in general formula (2), D is an oxygen atom, and k is 1. And L ² , L ³ and L ⁵ in the general formula (8) are C2-8 alkylene groups, and L ⁴ is a C2-20 alkylene group. Specific examples thereof include those having a repeating unit represented by the following formulas (9) and (10).

In formulas (9) and (10), J ⁻ represents a counter anion, and f represents an integer of 2 to 12.

  Other examples of the cationic polymer (b3) include those having a repeating unit represented by the following general formula (11).

In formula (11), A is a trivalent hydrocarbon group, and M, J ⁻ , R ³ , R ⁴ , R ^{4 ′} and d are the same as described above.
As the trivalent hydrocarbon group A, a C2-20 trivalent aliphatic hydrocarbon group, for example, a group represented by —CH ₂ (CH ₂ ) _g CH <(g is 0 or an integer of 1 to 18). , C6-12 trivalent aromatic hydrocarbon group, for example, a benzene ring in which the bonding position is 1,3,5-, 1,2,4- or 1,2,3-.
Examples of the cationic group (c2) include a group having a quaternary ammonium salt or a phosphonium salt. The group having a quaternary ammonium salt is preferably a divalent quaternary ammonium salt-containing heterocyclic group.
Examples of the divalent quaternary ammonium base-containing heterocyclic group include a divalent tertiary amino group-containing heterocyclic group [for example, a divalent imidazole ring group (1,4-imidazolene group, 2-phenyl-1,4-imidazolene). Group), divalent piperidine ring group (2,3-, 3,4- or 2,6-piperidylene group), divalent aromatic heterocyclic group (2,3-, 2,4-, 2,5). -, 2,6-, 3,4- or 3,5-pyridylene group, 2,5-pyrimidinylene group, 3,6-pyridazinylene group, 2,5-pyrazinylene group, etc.)] Groups.

The terminal structure of the cationic polymer (b3) is preferably a carbonyl group, a hydroxyl group or an amino group from the viewpoint of reactivity with the block of the polyolefin (a).
Mn of (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (a1) to (a6). Preferably, it is 1,200 to 8,000.

  The anionic polymer (b4) comprises a dicarboxylic acid (e1) having a sulfo group and a diol (b01) or a polyether (b1) as essential constituent units, and 2 to 80, preferably 3 to 60 in the molecule. Having one sulfo group.

(E1) is an aromatic dicarboxylic acid having a sulfo group, such as 5-sulfo-, 2-sulfo- and 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester forming properties thereof. Derivatives [lower alkyl (C1-4) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]; aliphatic dicarboxylic acids having a sulfo group, such as sulfosuccinic acid, ester-forming derivatives thereof [lower alkyl (C1-4 ) Esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]; and salts of these sulfo groups only [alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts, Ammonium salts, organic amine salts [mono-, di- and tri-alkyl (C1-4) amines -, Di- and triethylamine etc.), or amines having hydroxyalkyl (C2-4) groups (mono-, di- and triethanolamine, diethylethanolamine etc.) and the like, and quaternary ammonium salts of these amines etc.]; And a combination of two or more of these.
Of these, preferred are aromatic dicarboxylic acids (salts) having a sulfo group, and more preferred are 5-sulfoisophthalates (especially 5-sulfoisophthalic acid-sodium and -potassium).

Of the diol (b01) or polyether (b1) constituting the anionic polymer (b4), C2-10 alkanediol, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2-20), An EO adduct of bisphenol (such as bisphenol A) (addition mole number: 2 to 60) and a mixture of two or more of these.
Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (a1) to (a6). Preferably, it is 1,200 to 8,000.
Two or more of the above-described hydrophilic polymers (b) may be used in combination.

  Mn of (b) is preferably 150 from the viewpoint of heat resistance and reactivity with the block of polyolefin (a), more preferably 300, particularly preferably 1,000, most preferably 1,200, and preferred upper limit is 20,000, more preferably 18,000, particularly preferably 15,000, most preferably 8,000.

  The block polymer (BP) is at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond, in which the polyolefin (a) block and the hydrophilic polymer (b) block are included. Of these, a block polymer (BP1) in which (b) is a polyether (b1), (b) is preferred from the viewpoint of antistatic properties. Is a block polymer (BP3), which is a cationic polymer (b3), and (b) is a block polymer (BP4), which is an anionic polymer (b4).

  The block polymer (BP1) has a repeating unit represented by the following general formula (12).

In the formula (12), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30, particularly preferably 4 to 30); one of R ⁵ and R ⁶ is H and the other is H or methyl Group; y is an integer of 15 to 800 (preferably 20 to 500, more preferably 30 to 400); E ¹ , A ¹ , m and m ′ are as defined above; X and X ′ are represented by the following general formula (13), (14) and a corresponding group selected from (13 ′), (14 ′), that is, when X is a group represented by the general formula (13), X ′ is represented by the general formula (13 ′) It is a group shown, and the same relations apply to the general formulas (14) and (14 ′).

In the general formulas (13) and (14) and the corresponding formulas (13 ′) and (14 ′), R is the same as described in the above (b2) and is H or C1-4 (preferably 1 or 2); R ⁷ is a C 2-22 (preferably 3-16, more preferably 5-11) divalent hydrocarbon group, R ⁸ is H or C 1-10 (preferably 1-8, more preferably 1-6) alkyl group; r is an integer of 1-20 (preferably 1-15, more preferably 1-10), u is 0 or 1; Q, Q ′, T and T ′ are represented by the following formulae: Group represented by

In the above general formulas (15), (16) and the corresponding (15 ′), (16 ′), R ⁹ is H or C1-10 (preferably 1-8, more preferably 1-6); An alkyl group, R ¹⁰ is H or a methyl group, t is 1 when R ¹⁰ is a methyl group, and 0 when H is H.

Polyether segment {} in {} in the repeating unit represented by the general formula (12)
_{^{A 1) m O-E 1}} -O (A 1 O) m '} is a structure derived from the polyether diol (b1-1) or polyether diamine (b1-2), E ¹ of the formula , A ¹ , m and m ′ are the same as described above.

In the general formula (12), the terminal-modified polyolefin (a11) and / or the block polymer in which X is a group represented by the general formula (13) and X ′ is a group represented by the general formula (13 ′) (BP11) obtained by polymerizing (a12) and (b1-1), and (a11) and / or (a12) and (b1-2) obtained by polymerizing (BP12) And are included.
(BP11) (BP11-1) in which (a11) and (b1-1) are combined, (BP11-2) in which (a12) and (b1-1) are combined, and (BP11-1) A mixture of (BP11-2) is included. Similarly, (BP12) is a combination of (BP12-1), which is a combination of (a11) and (b1-2), (BP12-2) which is a combination of (a12) and (b1-2), and (BP12). -1) and a mixture of (BP12-2).

(BP11) is, for example, a method in which (b1-1) is added to (a11) and / or (a12) and a polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure, or uniaxial or biaxial In general, it can be produced by a method of polymerizing at 160 to 250 ° C. and a residence time of 0.1 to 20 minutes.
In the above polymerization reaction, various catalysts such as antimony catalysts (eg antimony trioxide); tin catalysts (eg monobutyltin oxide); titanium catalysts (eg tetrabutyl titanate); zirconium catalysts (eg tetrabutylzirconate); organic acids Metal salt catalysts [eg zirconium organic acid salts (eg zirconyl acetate) and zinc acetate]; and mixtures of two or more thereof. Among these, a zirconium catalyst and a zirconium organic acid salt are preferable, and zirconyl acetate is more preferable.
The amount of the catalyst used is preferably 0.001 to 5%, more preferably 0.01 to 3%, based on the total weight of (a11) and / or (a12) and (b1-1).

  Among (BP11), (BP11-2) may be reacted with (b11) after (a11) is secondarily modified with the above lactam or aminocarboxylic acid, or (a11) and lactam or An aminocarboxylic acid may be reacted in the presence of (b1-1) and subsequently reacted with (b1-1).

(BP12) except that the combination of (a11) and / or (a12) and (b1-1) in (BP11) is replaced with the combination of (a11) and / or (a12) and (b1-2) ( It can be produced by the same method as BP11).
Of (BP12), (BP12-2) may be produced by secondarily modifying (a11) with the lactam or aminocarboxylic acid and then reacting it with (b1-2).

In the general formula (12), the block polymer in which X is a group represented by the general formula (14) and X ′ is a group represented by the general formula (14 ′) includes (a13) (when r = 1) And / or (a14) (when r ≧ 2) and (b1-1) are subjected to a polymerization reaction (BP13), and (a13) and / or (a14) and (b1-2) (BP14) obtained by polymerization reaction.
(BP13) (BP13-1) combining (a13) and (b1-1), (BP13-2) combining (a13) and (b1-1), and (BP13-1) A mixture of (BP13-2) is included. Similarly, (BP14) is a combination of (BP14-1) in which (a13) and (b1-2) are combined, (BP14-2) in which (a14) and (b1-2) are combined, and (BP14) -1) and a mixture of (BP14-2).
(BP13) and (BP14) can be produced by the same method as (BP11) and (BP12).

The block polymer (BP3) has a block of the cationic polymer (b3), and has a structure in which the polyolefins (a) and (b3) are bonded alternately and repeatedly. (BP3) can be obtained by the polymerization reaction of (a1) to (a3) and (b3), and the polymerization reaction of (a11) and / or (a12) and (b1) in (BP1) It can be manufactured by a similar method. Moreover, (b3) and (b1) can be used together in arbitrary ratios (for example, weight ratio of 1: 9-9: 1) as needed.
The content of the cationic group (c2) in (BP3) is preferably 2 to 500, more preferably 10 to 300, particularly preferably 15 to 250 per molecule of (BP3) from the viewpoint of antistatic properties. is there. In addition, Mn of (BP3) per (c2) is preferably 120 to 30,000, more preferably 200 to 6,000, and particularly preferably 300 to 4,000 from the viewpoint of antistatic properties.

The block polymer (BP4) has a block of the anionic polymer (b4), and has a structure in which the polyolefins (a) and (b4) are bonded alternately and repeatedly. (BP4) can be obtained by the polymerization reaction of (a1) to (a3) and (b4), and can be produced by the same method as (BP1) above. Moreover, you may use together (b4) and (b1) in arbitrary ratios (for example, weight ratio of 1: 9-9: 1) as needed.
The content of the sulfo group in (BP4) is preferably 2 to 500, more preferably 10 to 300, and particularly preferably 15 to 250 per molecule of (BP4) from the viewpoint of antistatic properties. The Mn of (BP4) per sulfo group is preferably 120 to 30,000, more preferably 200 to 6,000, and particularly preferably 300 to 4,000 from the viewpoint of antistatic properties.

  The amount of (b) constituting the block polymer (BP) is preferably 20 to 90%, more preferably 25 to 80% based on the total weight of (a) and (b) from the viewpoint of antistatic properties. Especially preferably, it is 30 to 70%.

  The Mn of the block polymer (BP) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000 from the viewpoint of antistatic properties and dispersibility of the antistatic agent (B) in (A). Especially preferably, it is 8,000-30,000.

In the structure of (BP), the average number of repeating units (Nn) of the repeating units of the block (a) and the block (b) is the antistatic property and the dispersibility of the antistatic agent (B) in (A). From this viewpoint, it is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10.
Nn can be determined by Mn and ¹ H-NMR analysis of (BP).
For example, in the case of (BP11) having a structure in which the blocks of (a11) and (b1-1) are alternately and repeatedly bonded, 4.0 ^{1 to} 4.1 ppm ester bond { Since a signal attributed to protons of —C (C═O) —OCH ₂ —} and a signal attributed to protons of 3.2 to 3.7 ppm PEG can be observed, the ratio of these proton integral values is Thus, Nn can be obtained from this ratio and Mn.

  The terminal of (BP) is a carbonyl group, amino group and / or unmodified polyolefin terminal derived from (a) (polyolefin terminal not modified at all, ie, an alkyl group or alkenyl group), or a hydroxyl group derived from (b) And / or any amino group. Among these, an amino group is preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

[Carbodiimide compound (C)]
The carbodiimide compound (C) includes a carbodiimide monomer (C1) and a carbodiimide (co) polymer (C2). Among these, a carbodiimide (co) polymer (C2) is preferable from the viewpoint of dispersibility of (C) in (A) and / or (B).

The carbodiimide monomer (C1) is represented by the following general formula (17).

In the formula (17), R ¹¹ is a C1-20 aliphatic, alicyclic or aromatic monovalent hydrocarbon group.

  Examples of the carbodiimide monomer (C1) include dimethylcarbodiimide, diethylcarbodiimide, dipropylcarbodiimide, diisopropylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, bis (methylphenyl) carbodiimide, bis (dimethylphenyl) carbodiimide, and bis ( And dipropylphenyl) carbodiimide.

The carbodiimide (co) polymer (C2) has a repeating unit represented by the following general formula (18).

In the formula (18), R ¹² is an aliphatic, alicyclic or aromatic divalent hydrocarbon group.

Although the synthesis method of (C2) is not particularly limited, for example, a catalyst that promotes a carbodiimidization reaction of an isocyanate group using one or more of the following polyvalent polyisocyanate compounds (hereinafter referred to as a carbodiimidization catalyst) And abbreviation) can be synthesized.
Among the polyisocyanates, examples of the diisocyanate include the aromatic, aliphatic, alicyclic and araliphatic diisocyanates.
Examples of the trifunctional or higher polyisocyanate include phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2,5,4'-triisocyanate, triphenylmethane-2, 4 ′, 4 ″ -triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, diphenylmethane-2,4,2 ′, 4′-tetraisocyanate, diphenylmethane-2,5,2 ′, 5′-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methyl isocyanate), 3,5-dimethylcyclohexane-1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methylisocyanate And dicyclohexylmethane-2,4,2′-triisocyanate, dicyclohexylmethane-2,4,4′-triisocyanate, and the like.
Of these, diisocyanate is preferred from the viewpoint of ease of carbodiimidization reaction.

  Mn of (C2) is preferably Mn 400 to 500,000, more preferably Mn 1,000 to 200,000, and particularly preferably Mn 2,000 to 100,000.

Examples of the carbodiimidization catalyst include phospholene compounds (1-phenyl-2-phospholene-1-oxide, 1-phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide, 1-phenyl-3-methyl-2-phospholene-1-sulfide, 1-ethyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2- Phospholene-1-sulfide, 1-ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-methyl-3-methyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide, and these 3 Phospholene isomers), metal carbonyl complexes (pentacarbonyliron, nonacarbonyldiiron, tetracarbonylnickel, hexacarbonyltungsten, hexacarbonylchromium, etc.), acetylacetone complexes of metals (beryllium, aluminum, zirconium, chromium, iron, etc.), And phosphoric acid esters (trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tri-t-butyl phosphate, triphenyl phosphate, etc.). A carbodiimidization catalyst can be used individually by 1 type, or 2 or more types can also be mixed and used for it.
The amount of the catalyst used is preferably 0.001 to 30%, more preferably 0.01 to 10%, based on the weight of the polyisocyanate.

[Antistatic film]
The antistatic film of the present invention comprises the above (A) to (C), and based on the total weight of (A) to (C), (A) is 40 to 98 (preferably 55 to 95). )%, (B) 1-30 (preferably 3-25)%, and (C) 1-30 (preferably 2-20)%.
When the content of (A) is less than 40%, the mechanical properties of the film are deteriorated, and when it exceeds 98%, the antistatic property of the film is deteriorated; when the content of (B) is less than 1%, the antistatic property of the film is deteriorated. When the content exceeds 30%, the surface properties of the film deteriorate; when the content of (C) is less than 1%, the heat sealability of the film deteriorates, and when it exceeds 30%, the mechanical properties and appearance of the film deteriorate. .
The content of each component (A) to (C) in the film can also be estimated from the obtained film itself. That is, after observing the dispersion state in the film cross-section with a transmission electron microscope, image analysis [white portion in the observed image: (A), gray portion: (B), black portion: (C)] is performed, and an appropriate range (For example, the method of calculating | requiring by the area ratio in 10 micrometers x 10 micrometers) is mentioned. According to the above image analysis for films obtained from known charge ratios (weight ratios) (A) to (C), the area ratio and the charge weight ratio almost coincide.

  The antistatic film of the present invention can be obtained by molding a resin composition containing the above (A) to (C), and the resin composition has the purpose of further improving the antistatic property of the film. If necessary, at least one additive (D) selected from the group consisting of an alkali metal or alkaline earth metal salt (D1), a surfactant (D2) and an ionic liquid (D3) may be contained. .

  (D1) includes alkali acids (such as lithium, sodium and potassium) and / or alkaline earth metals (such as magnesium and calcium) organic acids (C1-12 mono- and dicarboxylic acids such as formic acid, acetic acid, propion) Salts of acids, oxalic acid and succinic acid; C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; and thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid and hydrobromic acid, Perchloric acid, sulfuric acid, nitric acid, phosphoric acid).

Specific examples of (D1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, and -calcium). Etc.), bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium) etc.], perchlorates (Such as lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (such as lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate ( Lithium methanesulfonate, -sodium, Potassium, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium and -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanes) Lithium fonate, -sodium, -potassium, -magnesium and -calcium), acetates (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfates (sodium sulfate, -potassium, -magnesium and -Calcium etc.), phosphate (sodium phosphate, -potassium, -magnesium, -calcium etc.), thiocyanate (potassium thiocyanate etc.), etc. are mentioned.
Of these, from the viewpoint of antistatic properties, preferred are halides, perchlorates, trifluoromethanesulfonates, acetates, and more preferred are lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium. And -sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, potassium acetate.

The amount of (D1) used is preferably 0.00 on the basis of the total weight of (A) and (B) from the viewpoint of an antistatic improvement effect and a film having a good appearance without being deposited on the resin surface. 001 to 3%, more preferably 0.01 to 2.5%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
The method of containing (D1) is not particularly limited, but it is preferable to disperse in the antistatic agent (B) in advance from the viewpoint of effective dispersion in the resin composition.
Further, when (D1) is dispersed in (B), it is particularly preferable that (D1) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (D1) is contained during the production of (B), and any time before production, during production, or immediately after production may be used.

Surfactant (D2) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohol (C8-18, the same hereinafter), higher fatty acid (C8-24, same hereinafter) or higher alkylamine (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18) To 8 or more, for example, EG, propylene glycol, glycerin, pentaerythritol and sorbitan) higher fatty acid ester EO adduct (molecular weight 250 or more and Mn 30,000 or less); higher fatty acid amide EO adduct (molecular weight 200 or more) And Mn 30,000 or less); and polyvalent alcohol EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn 30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [for example, many Fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

  As the anionic surfactant, compounds other than the above (D1) can be used, for example, carboxylates such as higher fatty acid salts; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; alkylbenzene sulfones. Examples thereof include sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate salts.

Cationic surfactants include quaternary ammonium salt types [eg, tetraalkyl (C4-100) ammonium salts (eg, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide and stearyltrimethylammonium bromide), Alkyl (C3-80) benzylammonium salts (eg lauryldimethylbenzylammonium chloride (benzalkonium chloride), alkyl (C2-60) pyridinium salts (eg cetylpyridinium chloride), polyoxyalkylene (C2-4) trialkylammonium salts (Eg, polyoxyethylenetrimethylammonium chloride) and sapamine type quaternary ammonium salts (eg, stearamide ester) Rudiethylmethyl ammonium methosulfate)]; and amine salt forms [eg higher aliphatic amines (C12-60, eg laurylamine, stearylamine, cetylamine, hardened tallow amine and rosinamine) inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and Phosphoric acid) salts or organic acids (C2-22, eg acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid and azelaic acid) salts, EO adducts of aliphatic amines (C1-30) Inorganic acids (above) or organic acids (above) and tertiary amines (C3-30, eg triethanolamine monostearate and stearamide ethyl diethyl methylethanolamine) Or salt of organic acid (above)].

Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, propionates of higher alkylamines (C8-24)], betaine type amphoteric surfactants [for example, higher alkyl (C12-18) dimethylbetaines, higher alkyldihydroxys. Ethyl betaine], sulfate ester type amphoteric surfactants [for example, sulfate esters of higher alkylamines (C8-24) and hydroxyethylimidazoline sulfate esters], sulfonate type amphoteric surfactants (eg, pentadecyl sulfotaurine salts) And imidazoline sulfonate) and phosphate ester type amphoteric surfactants [for example, phosphate ester salts of glycerin higher fatty acid (C8-24) esterified products].

These surfactants may be used alone or in combination of two or more.
Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); And ammonium salts [alkylamine (C1-20) and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts] and quaternary ammonium salts.
Of these, anionic surfactants are preferred from the viewpoint of antistatic properties, sulfonates are more preferred, alkylbenzene sulfonates (such as sodium dodecylbenzene sulfonate), alkyl sulfonates and paraffins are particularly preferred. Sulfonate.

The amount of (D2) used is preferably 0.001 to 5%, based on the total weight of (A) to (C), from the viewpoint of providing an antistatic property and a film having a good appearance without depositing on the resin surface. More preferably, it is 0.01 to 3%, Most preferably, it is 0.1 to 2.5%.
The method of containing (D2) is also not particularly limited, but it is preferable to disperse in the antistatic agent (B) in advance from the viewpoint of effective dispersion in the resin composition. Further, the timing when (D2) is dispersed in (B) is the same as in (D1).

  The ionic liquid (D3) is a compound other than the above (D1) and (D2), has a melting point of room temperature or lower, and at least one of cations or anions constituting (D3) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. Examples of the cation constituting (D3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

Examples of the amidinium cation include an imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.], imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-trimethylimidazolium etc.], tetrahydropyrimidinium cation [1,3-dimethyl-1,4
, 5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6- Tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and dihydropyrimidinium cation [1,3-dimethyl-1,4- or- 1,6-dihydropyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1 , 6-dihydropyrimidinium and the like].

Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.], guanidinium cation having an imidazolium skeleton [2-dimethyl Amino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl -3,4-diethylimidazolium etc.], tetrahydropyrimidiniu Guanidinium cation having a skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and guanidinium having a dihydropyrimidinium skeleton Cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium, etc.] And the like.

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

The amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more.
Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (D3), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester.
Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the organic and inorganic acids, Hamett acidity function initial conductivity standpoint preferred from of the anion constituting the (D3) of (D3) (-H ₀₎ is 12 to 100, the superacid conjugate base , Acids that form anions other than the conjugate bases of super strong acids, and mixtures thereof.

Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ions and poly (n = 1-25) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [eg methane sulfonic acid, dodecane sulfonic acid etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (eg trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane) Sulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Of these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (D3).
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, (D3) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (D3) used is usually 10% or less based on the total weight of (A) to (C), preferably from 0.001 in view of the good appearance and antistatic effect of the film and mechanical properties. 5%, more preferably 0.01 to 3%.
The method of adding (D3) is not particularly limited, but it is preferable to disperse in the antistatic agent (B) in advance from the viewpoint of effective dispersion in the resin composition. The timing when (D3) is dispersed in (B) is the same as in (D1) above.

  The production method of (D3) includes, for example, an amidinium cation and / or guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate, etc. Acid or inorganic acid] for acid exchange, or once the amidinium cation and / or guanidinium cation is hydrolyzed to form a monoamidoamine, then the monoamidoamine is converted to an acid (same as above) The method of neutralizing with is mentioned.

  The resin composition in the present invention contains at least one additive selected from the group consisting of a compatibilizing agent (E) and other additives for resin (F) as necessary as long as the effects of the present invention are not impaired. It can be included.

As the compatibilizer (E), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (E) used is preferably from 0.1 to 15%, more preferably from 1 to 10%, particularly preferably from the viewpoint of the mechanical strength of the film, based on the total weight of (A) to (C). Is 1.5-8%.
The method of containing (E) is not particularly limited, but it is preferable to disperse in the antistatic agent (B) in advance from the viewpoint of effective dispersion or dissolution in the resin composition.
The timing when (E) is dispersed or dissolved in (B) is the same as in (D) above.

  Other resin additives (F) include nucleating agent (F1), lubricant (F2), pigment (F3), dye (F4), mold release agent (F5), antioxidant (F6), flame retardant ( F7), an ultraviolet absorber (F8), an antibacterial agent (F9), a dispersant (F10), a plasticizer (F11), a conductive substance (F12), and a filler (F13). Can be mentioned.

Examples of the nucleating agent (F1) include organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-t -Butylphenyl) phosphate and sodium benzoate] and inorganic nucleating agents (eg graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, Alumina, barium sulfate and calcium sulfate).
Lubricants (F2) include waxes (eg carnauba wax, paraffin wax and polyolefin wax), higher fatty acids (C8-24, eg stearic acid, oleic acid, linoleic acid and linolenic acid), higher alcohols (C8-18, eg stearyl). Alcohols, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol and behenyl alcohol) and higher fatty acid amides (C8-24, such as stearic acid amide, oleic acid amide, linoleic acid amide and linolenic acid amide).

Examples of the pigment (F3) include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (oxidation). Chromium, lead chromate, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lakes, monoazos, disazos, chelate azos, etc.), polycyclic pigments (benzoimidazolones) Phthalocyanine, isoindolinone, anthraquinone, etc.).
Examples of the dye (F4) include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline.
As the release agent (F5), lower fatty acid (C1-4) alcohol ester (for example, butyl stearate) of higher fatty acid (above), polyvalent (divalent to tetravalent or higher) of fatty acid (C2-18) ) Alcohol esters (eg hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (eg EG monostearate) and liquid paraffin.

  Antioxidants (F6) include phenolic {eg monocyclic phenols [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenols [eg 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol and 4,4′-thiobis (3-methyl) -6-tert-butylphenol] and polycyclic phenols [ For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-) 5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane]}; sulfur-based [eg, dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, dimyristyl 3,3'- Thiodipropionate, distearyl β, β'-thiodibutyrate and dilauryl sulfide]; phosphorus systems [eg triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t) -Butylphenylditridecyl) phosphite, cyclic neopentanetetri Bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butyl) Phenyl) phosphite and diisodecyl pentaerythritol diphosphite]; and amine systems such as octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, N, N-bis ( 1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine and phenothiazine.

  The flame retardant (F7) includes a halogen-containing flame retardant (F71), a nitrogen-containing flame retardant (F72), a sulfur-containing flame retardant (F73), a silicon-containing flame retardant (F74), and a phosphorus-containing flame retardant (F75). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (F71) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, Hexabromocyclododecane, etc .;

Examples of the nitrogen-containing flame retardant (F72) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid;
Examples of the sulfur-containing flame retardant (F73) include sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters and amides thereof;
Examples of the silicon-containing flame retardant (F74) include polyorganosiloxane;

  Examples of the phosphorus-containing flame retardant (F75) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphate, halogen-containing phosphate, phosphorous acid, phosphonate, and ammonium phosphate.

Examples of the phosphate include phosphate [trialkyl (alkyl group is C1-12) phosphate and the like], condensed phosphate [trialkyl (alkyl group is C1-12) poly (n = 2 to 30) phosphate and the like];
Examples of the halogen-containing phosphate include tris alkyl halide (alkyl group is C2-4) phosphate and the like;
Examples of the phosphonate include phosphonate [trialkyl (alkyl group is C1-12) phosphonate, etc.], condensed phosphonate [trialkyl (alkyl group is C1-12) poly (n = 2-30) phosphonate, etc.];
As the ammonium phosphate, those usually marketed for flame retardants can be used. These may be used in combination with a melamine compound (for example, melamine alone), a pentaerythritol compound (for example, pentaerythritol, dipentaerythritol), an amide (for example, nylon 6, nylon 66), or the like as necessary.

The flame retardant may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.
Of the above flame retardants, (F72) is preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  Examples of the ultraviolet absorber (F8) include benzotriazoles [for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], Benzophenone series [eg 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate series [eg phenyl salicylate and EG monosalicylate] and acrylate series [eg 2-ethylhexyl-2-cyano -3,3'1-diphenyl acrylate].

  Examples of the antibacterial agent (F9) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt), organic iodine (for example, 4-chlorophenyl-3-iodopropargyl). Formal), nitrile (eg, 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg, methylene bisthianocyanate), N-haloalkylthioimide (eg, N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agent (Eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo- 2-propenyl Til carbonate), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecylammonium chloride) and pyridine compounds [eg 2,3,5,6- Cytochloro-4- (methylsulfonyl) -pyridine].

  As the dispersant (F10), a dispersant of Mn 1,000 to 100,000, for example, naphthalene sulfonic acid formalin condensate (Mn 1,000 to 10,000), polystyrene sulfonate metal [for example, alkali metals (for example, sodium and potassium) ] Salt (Mn 1,000-100,000), polyacrylic acid metal [for example, alkali metal (same as above)] salt (Mn 2,000-50,000), carboxymethyl cellulose and polyvinyl alcohol.

Examples of the plasticizer (F11) include mono- and diesters containing polyoxyalkylene chains, polyester polyols, polyether polyols, aromatic carboxylic acid esters [C10-28, such as phthalic acid esters (for example, dioctyl phthalate and dibutyl phthalate, di-2). -Ethylhexyl phthalate etc.)], aliphatic monocarboxylic acid esters [C3-30, such as methylacetylricinoleate and triethylene glycol dibenzoate], aliphatic dicarboxylic acid esters [C8 or more and Mn2,000 or less, such as di (2- Ethylhexyl) adipate and adipic acid-propylene glycol-based polyester (Mn 200 to 2,000)], aliphatic tricarboxylic acid ester [eg citrate ester (eg triethyl citrate)] Phosphoric acid triester [e.g. triphenyl phosphate] and petroleum resins.

  Examples of the conductive substance (F12) are compounds other than the above (D1) and (D3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  Examples of the filler (F13) include inorganic fillers (eg, calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker and titanium whisker). And organic fillers [for example, urea, calcium stearate and organic crosslinked fine particles (for example, epoxy-based and urethane-based)].

The total use amount of (F) is usually 45% or less based on the total weight of (A) to (C), preferably 0.001 to 40% from the viewpoint of the effect of each additive and the mechanical properties of the film. More preferably, it is 0.01 to 35%, and particularly preferably 0.05 to 30%.
Of (F), (F9), (F10), (F11) and (F13) are each usually 10% or less, preferably 1 to 5%; (F7) is usually 20% or less, preferably 1 to 10%. (F3), (F4) and (F12) are usually 5% or less, preferably 0.1 to 3%; (F1), (F2), (F5), (F6) and (F8) are usually 3% Hereinafter, it is preferably 0.05 to 1%.

The film containing (A) to (C) of the present invention can be obtained by molding the resin composition according to, for example, the following steps. Further, as described later, a multilayer film can be formed using the film as at least a surface layer.
1. Production of film <1> (A) to (C) and optionally added (D) to (F) mixing step;
<2> Film forming step;
<3> Cooling step using rolls or the like;
<4> Stretching step (performed as necessary)
In addition, a film made of a thermoplastic resin (G) and / or the film of the present invention can be used as a base layer, and a multilayer film formed by laminating the film of the present invention as a surface layer on one or both sides of the base layer can also be formed. .
Here, the thermoplastic resin (G) includes those described later including the polyolefin resin (A) in the present invention, and the film made of the thermoplastic resin (G) constituting the above-mentioned base layer includes the film in the present invention. The antistatic agent (B) may or may not be included.

  In addition to the polyolefin resin (A), the thermoplastic resin (G) includes polyacetal resin (G1); vinyl resin [polyacrylic resin (G2) [for example, polymethyl methacrylate]; polystyrene resin (G3) [vinyl group A copolymer comprising, for example, polystyrene, containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS Resin)] etc.]; polyester resin (G4) [for example Ethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resin (G5) [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; polycarbonate resin (G6) [for example, polycarbonate, polycarbonate / ABS alloy resin]; polyphenylene ether resin (G7); biodegradable resin (G8), and a mixture of two or more thereof Is mentioned.

When laminating, the surface layer film may be laminated on one side or both sides of the base layer, and the type of the surface layer resin when laminating on both sides may be the same or different, and the type of resin on each of the front and back sides of the base layer Different films may be laminated in multiple layers (2-6 layers or more). Further, the base layer may be a multilayer film in which the units of the film made of the thermoplastic resin (G) -the film of the present invention are repeated.
Alternatively, either or both of the surface layer and the base layer may be a foamed layer or a multilayer film composed of a foamed layer and a non-foamed layer, or a multilayer film in which at least one of the surface layer and the base layer is stretched uniaxially or multiaxially.

The film production process will be described in more detail below.
<1> Mixing step The mixing method of the resin composition is not particularly limited.
(1) A method in which (A), (B), (C) and, if necessary, (D) to (F) are dry blended with a tumble mixer, ribbon blender, Henschel mixer or the like and mixed,
(2) A method of dry blending each of the above components by the above method, followed by melt mixing (usually 200 to 280 ° C.) with an extruder and pelletizing,
(3) A part of (A), the masterbatch resin composition of (B) and (C) was prepared in advance by melt mixing (200 to 280 ° C.) using an extruder [in the masterbatch resin composition ( The content of B) is preferably 30 to 70% by weight], and the master batch, the remaining (A) and, if necessary, (D) to (F) may be dry blended with the above mixer and mixed.
Among these methods, the methods (2) and (3) are preferable from the viewpoint of dispersibility of (B) into (A), and the method (2) is particularly preferable. In the resin composition for forming a film in the present invention, (A) and (B) are excellent in compatibility, so that a good film can be obtained even by the method (1).

<2> Film-forming step The film-forming method is not particularly limited, and various film-forming methods (for example, an extrusion molding method, an inflation method, and a tubular method) can be used.
In either method, a resin composition is laminated from a die that can be co-extruded to form a film, or a surface layer is laminated to the base layer, or the surface layer and the base layer are bonded together using an adhesive or an adhesive layer. It is good also as a multilayer film.
A foaming layer can also be formed in the film by adding a foaming agent (for example, methyl chloride, butane, carbon dioxide and azobisisobutyronitrile) during film formation.

In coextrusion, for example, the temperature of the resin composition is preferably 85 to 280 ° C., and the die temperature is preferably 180 to 280 ° C.
In the case of laminating the surface layer on the base layer, for example, the layers may be laminated and then thermocompression bonded, or the respective bonding surfaces may be preliminarily heated with a heating device and then bonded and pressure bonded.
The adhesive used in the bonding method is not particularly limited. For example, an ethylene-vinyl acetate copolymer and a methyl methacrylate polymer elastomer [for example, trade names: Tufprene and Tuftec [both manufactured by Asahi Kasei Kogyo Co., Ltd.] ] Is preferred.

<3> Cooling step by rolls etc. As for the cooling method, for example, a method of cooling by contact with a roll (for example, extrusion method) and a method of cooling by blowing air (for example, an inflation method and a tubular method) are used. Can be used.

<4> Stretching step As a stretching method, for example, after forming a non-stretched film in advance, a method of stretching in a separate step (for example, a method of stretching using a difference in peripheral speed of rolls and a tenter method) and a film Examples of the production process include a stretching process (for example, an inflation method and a tubular method).

  In any stretching method, the stretching ratio is preferably 2 to 20 times in the case of uniaxial stretching and 2 to 15 times in each direction in the case of biaxial stretching, from the viewpoint of antistatic properties. The antistatic resin film of the present invention can exhibit further excellent antistatic properties through the stretching step.

In addition, the antistatic film of the present invention can be used depending on the purpose (for example, printing on a film and adhesion of the film to other objects) and purpose (for example, improvement in fixing property of printing ink or film adhesion). Surface treatments such as corona treatment and flame treatment can also be performed.
The surface to be surface-treated may be the surface of the antistatic surface layer or the back surface side (base layer surface) where the antistatic surface layer is not laminated (in the case of one-side lamination).

  In the case of laminating, it may be a multilayer sheet, may contain a foamed layer, or may be stretched, as in the production of the film.

The film of the present invention has excellent mechanical properties and permanent antistatic properties, as well as good paintability and printability.
Examples of the method for applying the film include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method.
Examples of the method for printing on the film include various printing methods such as gravure printing, flexographic printing, screen printing, and offset printing.
Examples of the printing ink include those usually used for printing plastics.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.

Production Example 1 [Production of acid-modified polyolefin (a-1)]
To a stainless steel autoclave, the thermal degradation method [density 0.90 g / cm ^{3 at} 23 ° C.,
Low molecular weight ethylene / propylene random copolymer (Mn3) obtained by thermal degradation of ethylene / propylene (random addition) copolymer (ethylene content 2%) of MFR 6.0 g / 10 min at 410 ± 0.1 ° C.] , 500, density 0.89 g / cm ³ , 7.1 double bonds per 1,000 C, average number of double bonds per molecule 1.8, content of polyolefin that can be modified at both ends 90 %) 95 parts, maleic anhydride 10 parts and xylene 30 parts were charged, melted at 200 ° C. in a nitrogen gas atmosphere (sealed), and reacted at 200 ° C. for 20 hours.
Thereafter, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polyolefin (a-1). The acid value of (a-1) was 27.2, and Mn was 3,700.

Production Example 2 [Production of secondary modified polyolefin (a-2)]
A stainless steel autoclave was charged with 66 parts of (a-1) and 34 parts of 12-aminododecanoic acid, melted at 200 ° C. in a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under a reduced pressure of 1.3 kPa or less. Secondary modified polyolefin (a-2) was obtained. The acid value of (a-2) was 17.7, and Mn was 5,700.

Production Example 3 [Production of Antistatic Agent (B-1) Consisting of Block Polymer]
Reduce the terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl groups at both ends of PEG with (a-2) 73.3 parts, Mn 2,000, volume resistivity 1 × 10 ⁷ Ω · cm into a stainless steel autoclave. 26.7 parts of a hydrophilic polymer (volume resistivity 2 × 10 ⁸ Ω · cm) (b-1) modified to a primary amino group and an antioxidant [trade name “Irganox 1010”, Ciba Specialty Made by Tea Chemicals. same as below. 0.3 parts were charged and polymerized for 3 hours under the reduced pressure of 220 ° C. and 0.13 kPa or less to obtain a viscous polymer. The polymer was taken out on a belt in the form of a strand and pelletized to obtain an antistatic agent (B-1) comprising a block polymer.

Production Example 4 [Production of Cationic Polymer (b-2) (Hydrophilic Polymer)]
A glass autoclave was charged with 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate. After purging with nitrogen, the temperature was raised to 220 ° C. over 2 hours and reduced to 0.13 kPa over 1 hour. The polyesterification reaction was performed. After completion of the reaction, the reaction mixture was cooled to 50 ° C. and dissolved by adding 100 parts of methanol. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 31 parts of dimethyl carbonate was gradually added dropwise over 3 hours, and aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Subsequently, the solvent was distilled off under reduced pressure, and a cationic polymer (b-2) having an average of 12 quaternary ammonium groups (hydroxyl value 30.1, acid value 0.5, volume resistivity 1 × 10 ⁵ Ω · cm) Got.

Production Example 5 [Production of antistatic agent (B-2) comprising block polymer]
(A-2) 63.0 parts, (b-2) 37.0 parts, antioxidant 0.3 parts and zirconyl acetate 0.5 parts were added to a stainless steel autoclave at 230 ° C. and 0.13 kPa or less. Polymerization was performed for 4 hours under reduced pressure to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (B-2) comprising a block polymer.

Production Example 6 [Production of Anionic Polymer (b-3) (Hydrophilic Polymer)]
A stainless steel autoclave was charged with 67 parts of PEG of Mn300, 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide, and the temperature was raised to 190 ° C. under a reduced pressure of 0.67 kPa, and methanol was distilled off. An anionic polymer (b-3) having an average of 5 sodium sulfonate bases in one molecule (hydroxyl value 29.6, acid value 0.4, volume resistivity 2 × 10 ⁶ Ω · cm).

Production Example 7 [Production of antistatic agent (B-3) comprising block polymer]
In Production Example 5, instead of (a-2) 63.0 parts and (b-2) 37.0 parts, (a-2) 62.6 parts and (b-3) 37.4 parts were used. Obtained the antistatic agent (B-3) which consists of a block polymer like manufacture example 5. FIG.

Production Example 8 [Production of antistatic agent (B-4) comprising block polymer]
Instead of (a-2) 73.3 parts and (b-1) 26.7 parts in Production Example 3, (a-2) 77.9 parts, polytetramethylene glycol (Mn1,800, volume resistivity) 1 × 10 ¹¹ Ω · cm) (b-4) An antistatic agent (B) comprising a block polymer in the same manner as in Production Example 3, except that 0.5 part of zirconyl acetate was added. -4) was obtained.

Examples 1-6, Comparative Examples 1-6
Extruder with a T-die according to the composition shown in Table 1 [Cylinder temperature: 220 ° C. when using (A-1), 180 ° C. when using (A-2), and (A-3) using Is 150 ° C. same as below. ] And melt-extruded by a cooling roll of 20 ° C. to obtain an extruded film (single layer film) having a thickness of 100 μm.

Examples 7-13, Comparative Examples 7-13
Extruder equipped with a T-type die capable of coextruding two types and three layers of the base layer (X) and the surface layer (Y) according to the composition shown in Table 2 [Cylinder temperature is the same as above. The cylinder temperature when two types of (A-1) to (A-3) are used is the higher temperature. ] (70) -thick (Y) / (X) / (Y) -type extruded film (3-layer film) having a surface layer (Y) of 10 μm on the front and back surfaces by quenching with a cooling roll at 20 ° C. did.

(note)
A-1: Polypropylene resin [Brand name: Novatec PP F203T, manufactured by Nippon Polypro Co., Ltd.]
A-2: Polyethylene resin [Brand name: Novatec LL UJ960, manufactured by Nippon Polyethylene Co., Ltd.]
A-3: Ethylene / vinyl acetate copolymer resin [Brand name: Novatec EVA LV430, manufactured by Nippon Polyethylene Co., Ltd.]
G-1: Nylon resin [Brand name: Ube Nylon 1013B, manufactured by Ube Industries, Ltd.]
G-2: Cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer (polyester resin) [trade name: EASTER PETG6763, manufactured by Eastman Chemical Japan Co., Ltd.]
C-1: Carbodiimide compound [Carbodilite LA-1], manufactured by Nisshinbo Co., Ltd.]
C-2: Carbodiimide compound [Carbodilite HMV-8CA], manufactured by Nisshinbo Co., Ltd.]
D-1: 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate D-2: sodium dodecylbenzenesulfonate

[Performance tests, etc.]
About the film obtained above, performance evaluation etc. were performed based on the following test method. The results are shown in Table 3.
[1] Antistatic property [Conforms to ASTM D257 (1984)]
Evaluated by surface resistivity (unit: Ω). Each test piece (100 × 100 mm) cut out from the film was used, and the test piece was allowed to stand for 48 hours under the conditions of 23 ° C. and humidity 50% RH. ] Under the same conditions.

[2] Heat sealability [conforms to JIS Z-0238]
Two films are stacked and stacked, and a thermal inclination tester [manufactured by Toyo Seiki Co., Ltd.] is used to perform thermocompression bonding [temperature: the combined surfaces are (A-1), (A-2) or (A-3). ) Is used at 160 ° C., 140 ° C. or 90 ° C., pressure: 3 kg / cm ² , time: 1 second], then the test piece is allowed to stand at 23 ° C. and humidity 50% RH for 24 hours, and then pulled. The test is performed in the same manner as in the test [based on JIS K7127-1989], and the breaking strength (unit: kg / 15 mm) of the heat seal portion is measured.

[3] Surface roughness [conforms to JIS B0601-2001]
The surface was subjected to centerline average roughness described in Appendix 2 of JIS B0601: 2001 under the conditions of a magnification of 1,250 times using a shape measurement microscope [VD-8550, manufactured by Keyence Corporation]. (Ra) (unit: μm) was measured at five locations, and the average of these was used as an index. The smaller the numerical value, the smaller the surface roughness and the better. Surface roughness is evaluated by surface roughness.

[4] Contamination property of glass plate A test piece (100 × 100 mm) cut out from a film and two glass plates (120 × 120 × 2 mm) are sufficiently obtained using ultrapure water (specific resistance 17.5 MΩ · cm), respectively. Then, it is dried in an air circulation dryer at 50 ° C. for 2 hours. The test piece is put in close contact with the two glass plates from the front and back surfaces, and a 1 kg weight is placed on the glass plate on one side, and left still at 60 ° C. and 90% RH for 7 days. Then, a test piece is removed, the test piece contact surface of a glass plate is observed, and glass plate contamination property is evaluated by the presence or absence of a deposit. The presence or absence of film surface deposits is evaluated based on the glass plate contamination.

Evaluation criteria ○: No deposit on glass plate
×: There is a deposit on the glass plate.

[5] Area ratio of components by image analysis of cross section of single layer or surface layer film Transmission electron microscope shows dispersion state of components (A) to (C) in each cross section of surface layer film in single layer film or three layer film Each area ratio of (A) to (C) is measured using image analysis measurement software [trade name “WinROOF”, manufactured by Mitani Corporation] for the range of 10 μm × 10 μm of the obtained image. %).

  As is apparent from Table 3, the antistatic film of the present invention is superior in heat sealability, permanent antistatic properties, and surface characteristics as compared with a film formed by molding a comparative resin composition. I understand.

  Since the antistatic film of the present invention is excellent in antistatic properties and heat sealing properties, it can be used as a packaging material (packaging bags for foods such as instant foods and mayonnaise, individual packaging bags for cigarettes, cleaning bags, and plastic case films. , Packaging bags for electrical parts, etc.), covering materials (print laminates laminated on paper, protective films for flexible disks, agricultural materials, etc.), tape materials (tape substrates for semiconductor manufacturing processes, etc.) and other antistatic properties and heat sealing It is extremely useful as various materials in a wide range of fields that require high performance.

Claims (5)

It contains the following (A) to (C), and based on the total weight of (A) to (C), (A) is 40 to 98%, (B) is 1 to 30%, and (C) is An antistatic film containing 1 to 30%.
(A) Polyolefin resin.
(B) Polyolefin (a) block and volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω
-Antistatic agent (C) carbodiimide compound comprising a block polymer having a structure in which blocks of hydrophilic polymer (b) of cm are repeatedly and alternately bonded The film according to claim 1, further comprising at least one additive (D) selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant and an ionic liquid. An antistatic multilayer film comprising a film made of a thermoplastic resin and / or a film according to claim 1 or 2 as a base layer, and the film according to claim 1 or 2 is laminated as a surface layer on one side or both sides of the base layer. A film article obtained by coating and / or printing the film according to claim 1. Structure in which a block of polyolefin resin (A) and polyolefin (a) and a block of hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are alternately and repeatedly bonded. A carbodiimide compound (C) is contained in an antistatic film comprising an antistatic agent (B) comprising a block polymer having the above-described method, and the method for improving the heat sealability of the film.