JP5340578B2 - Antistatic agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic agent, which imparts excellent antistaticity to a thermoplastic resin, without impairing mechanical properties of the thermoplastic resin, and an antistatic resin composition. <P>SOLUTION: The antistatic agent (X) comprises a copolymer (A) containing as a composing unit a block of a polyether (a) having an HLB of 16 to 20 and composed of a mixture of two or more polyethers (aE) having oxyethylene groups, or a mixture of at least one polyether (aE) having oxyethylene groups and one polyether (anE) having no oxyethylene group. The crystallinity degree of the oxyethylene group part of (A), measured by the differential scanning calorimetry (DSC), is 0 to 30%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an antistatic agent. More specifically, the present invention relates to an antistatic agent that imparts excellent antistatic properties to a thermoplastic resin without impairing mechanical properties.

  Conventionally, as a method for imparting permanent antistatic property to a thermoplastic resin, a method of adding an antistatic agent having a polyoxyalkylene chain to the thermoplastic resin is known. (For example, see Patent Documents 1 and 2)

Japanese Patent Laid-Open No. 03-255161 Japanese Patent Laid-Open No. 03-258850

However, when the content of the polyoxyethylene chain is increased for the purpose of improving the above-mentioned prior art or antistatic properties, the effect of improving the antistatic properties is insufficient, and conversely, the mechanical properties of the thermoplastic resin are reduced. There was a problem of causing adverse effects.
An object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to a thermoplastic resin without impairing the mechanical properties of the thermoplastic resin.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a mixture of two or more polyethers (aE) having an oxyethylene group, or at least one polyether (aE) having an oxyethylene group and a polyether having no oxyethylene group. (A) comprising a copolymer (A) comprising a block of a polyether (a) of HLB 16-20, comprising a mixture with (anE), and measured by a differential scanning calorimetry (DSC) method (A) An antistatic agent (X), wherein the oxyethylene group portion has a crystallinity of 0 to 30%; an antistatic resin composition comprising the thermoplastic resin (B) containing the antistatic agent A molded article formed by molding the composition; and a molded article obtained by painting and / or printing the molded article.

The antistatic agent of the present invention and a molded product containing the antistatic agent have the following effects.
(1) The antistatic agent can impart excellent antistatic properties to the thermoplastic resin.
(2) The molded article has excellent permanent antistatic properties and excellent mechanical properties.

[Polyether]
The polyether constituting the polyether (a) in the present invention includes a polyether diol (a1) and a polyether diamine (a2) from the viewpoint of the type of terminal group, and the presence or absence of an oxyethylene group. From the viewpoint, polyethers having an oxyethylene group (aE) and polyethers having no oxyethylene group (anE) are included.

The polyether diol (a1) is obtained by subjecting the diol (a01) or the dihydric phenol (a02) to an addition reaction of alkylene oxide (hereinafter abbreviated as AO) [carbon number (hereinafter abbreviated as C) 2 to 12]. Examples of the structure include those represented by the 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 (a01) or (a02), and A ¹ is C2-12 (preferably 2-8, more preferably 2) which may contain a halogen atom. -4) alkylene group; m and m 'represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 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.

Diol (a01) includes C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohol (aliphatic, alicyclic and araliphatic dihydric alcohol) and C1-12 tertiary. Examples include amino group-containing diols.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter, EG, PG, 1,4-BD, 1,6-HD, NPG) and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, 1,3-cyclopentanediol, and the like.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

Tertiary amino group-containing diols include aliphatic or alicyclic primary monoamines (C1-12, preferably 2-10, more preferably 2-8) bishydroxyalkyl (alkyl group C1-12, preferably 2-10, more preferably 2-8) and bishydroxyalkyl (alkyl group C1-12) compounds of aromatic (aliphatic) primary monoamines (C6-12).
The bishydroxyalkylated monoamine can be obtained by a known method, for example, by reacting monoamine with C2-4 AO [ethylene oxide, propylene oxide (hereinafter abbreviated as EO, PO, respectively), butylene oxide, etc.] It can be easily obtained by reacting with 12 halogenated hydroxyalkyl (2-bromoethyl alcohol, 3-chloropropyl alcohol, etc.).

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

  As the dihydric phenol (a02), C6-18 (preferably 8-18, more preferably 10-15), for example, monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F, -S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydrokibiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

  Of (a01) and (a02), from the viewpoint of antistatic properties, preferred are dihydric alcohols and dihydric phenols, more preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are EG and bisphenol A.

As AO to be subjected to addition reaction with diol (a01) or dihydric phenol (a02), C2-12, for example, EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran (hereinafter referred to as THF) (Abbreviation) and a mixture of two or more of these, other AO and substituted AO may be used together if necessary.
Examples of other AO and substituted AO include epoxidized products of C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of the other AO and substituted AO used is preferably 30% or less, more preferably 0 to 25%, particularly preferably 0 to 20% based on the weight of the total AO from the viewpoint of antistatic properties. is there.

The number of added moles of AO is preferably 1 to 300 moles, more preferably 2 to 250 moles, more preferably 2 to 250 moles per hydroxyl group of (a01) or (a02), from the viewpoint of the volume resistivity value of polyether diol (a1). 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 by a known method, for example, in the presence of an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) under the conditions of 100 to 200 ° C. and pressure of 0 to 0.5 MPaG.

  The content of the oxyalkylene unit in the polyether diol (a1) is preferably 5 to 99.8%, more preferably 8 to 99.% from the viewpoint of the volume resistivity value of (a1) based on the weight of (a1). 6%, particularly preferably 10 to 98%. Further, when (a1) contains a polyoxyethylene group, the content of oxyethylene units in the polyoxyalkylene is preferably 5 to 5 from the viewpoint of the volume resistivity value of (a1) based on the weight of the polyoxyalkylene. 100%, more preferably 10 to 100%, particularly preferably 50 to 100%, most preferably 60 to 100%.

The polyether diamine (a2) has a structure in which the hydroxyl group of the polyether diol (a1) is modified to an amino group (primary or secondary amino group), for example, a general formula: RNH-A ^2- (OA ¹ ) those represented by ^{_{m O-E 1 -O (A}} 1 O) m '-A 2 -NHR the like.
Therefore, the content of oxyalkylene units in (a2) and the preferred content are the same as the corresponding content of oxyalkylene units in (a1), and the polyoxyethylene chain in the case where (a2) contains a polyoxyethylene chain. The content and preferred content of oxyethylene units in the alkylene are the same as in the case of (a1).

Symbols E ¹ , A ¹ , m and m ′ in the formula are the same as above, and A ² is a C 2-12 (preferably 2-8, more preferably 2-4) optionally containing a halogen atom. Represents an alkylene group, and m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and a bond when these are composed of two or more oxyalkylene units The format may be random and / or block. R represents H or a C1-4 (preferably 1 or 2) alkyl group.

(A2) can be easily obtained by changing both terminal hydroxyl groups of (a1) to amino groups by a known method.
As a method for changing a hydroxyl group to an amino group, a known method, for example, a method in which a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group in (a1) is reduced to form an amino group [for example, (a1) and acrylonitrile And a method of hydrogenating the resulting cyanoethylated product], a method of reacting (a1) with an aminocarboxylic acid or lactam, a method of reacting (a1) with a halogenated amine under alkaline conditions, and the like. .

Next, a polyether (aE) having an oxyethylene group and a polyether (anE) having no oxyethylene group will be described.
The polyether (aE) having an oxyethylene group has an oxyethylene group in the molecule among the (a1) and (a2), and is added to the diol (a01) or the dihydric phenol (a02). Is one or more types of AO other than EO and EO, the addition format may be either block and / or random.
Polyether (anE) having no oxyethylene group is one having no oxyethylene group in the molecule among (a1) and (a2), and is added to the diol (a01) or dihydric phenol (a02). When two or more types of AOs are used, the addition format may be block and / or random.

  Number average molecular weight of the above polyether [hereinafter abbreviated as Mn, measurement is by gel permeation chromatography (GPC) method described later. ] Is preferably 200 to 20,000, more preferably 250 to 10,000, and particularly preferably 300 to 5,000.

[Polyether (a)]
The polyether (a) in the present invention composed of the above polyether is a mixture (I) of two or more polyethers (aE) having an oxyethylene group, or at least one kind having an oxyethylene group. It consists of a mixture (II) of polyether (aE) and polyether (anE) having no oxyethylene group.
The types in the mixture (I) include, for example, the types of initiators [the diol (a01), dihydric phenol (a02), etc.], types of terminal groups (hydroxyl groups, amino groups, etc.), AO addition moles, and types of AO. , And different AO addition formats (random and / or block etc.) are different.
Moreover, the kind in mixture (II) refers to the thing different similarly to the said mixture (I) in addition to the presence or absence of oxyethylene group containing.
The degree of crystallinity measured by the method described later can be adjusted by combining different types of polyethers in the mixture (I) or (II).

  The proportion of the polyether (aE) having an oxyethylene group is preferably 80 to 100%, more preferably 82 to 100, from the viewpoint of antistatic properties and mechanical properties of the molded product based on the total weight of the polyether (a). %, More preferably 85 to 100%.

The polyether (a) in the present invention has an HLB of 16 to 20 (preferably 17 to 20). When the HLB is less than 16, the antistatic property deteriorates. The HLB in (a) can be adjusted to the above range by selecting the kind of polyether constituting (a).
Here, HLB is an abbreviation for Hydrophile-Lipophile Balance and represents a balance between hydrophilicity and lipophilicity, and is generally referred to as HLB of Griffin. Specifically, the HLB is obtained from the following formula [Refer to New Surfactant, Sanyo Chemical Industries, October 1996, 4th edition].

HLB = (molecular weight of hydrophilic group portion / total molecular weight) × 100/5

[Antistatic agent (X)]
The antistatic agent (X) of the present invention comprises a copolymer (A) having the above-mentioned polyether (a) block as a structural unit.
As (A), polyether ester amide (A1), a block polymer (A2) having a structure in which a polyolefin block and a polyether block are alternately and repeatedly bonded, polyether amide imide (A3), epihalohydrin / AO copolymer (A4), polyether ester (A5), methoxypolyethylene glycol (meth) acrylate copolymer (A6), polyether-containing ethylene / vinyl acetate copolymer (A7), and mixtures of two or more thereof Etc.
Of these, (A1) to (A5) are preferable from the viewpoint of antistatic properties, and (A1) and (A2) are more preferable.

  As (A1), for example, in the polyether ester amide described in JP-A-6-287547 and JP-B-4-5691, the polyether (1a) constituting the polyether ester amide is the polyether in the present invention. What is contained in (a) is mentioned. Among these, from the viewpoint of heat resistance, a polyether ester amide derived from polyamide (m) and a polyether composed of an AO adduct of bisphenol compound (Mn 300 to 5,000) and / or polyalkylene glycol is preferable. It is.

The measurement conditions of Mn are as follows, and Mn in the present invention is measured under the same conditions.
Apparatus: High-temperature gel permeation chromatography solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

Examples of the polyamide (m) include (1) lactam ring-opening polymers, (2) polycondensates of aminocarboxylic acids, and (3) polycondensates of dicarboxylic acids and diamines.
Among the amide-forming monomers that form these polyamides, the lactam in (1) includes C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid in (2), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid.
Examples of the dicarboxylic acid in (3) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [acid anhydrides, lower (C1-4) alkyl esters, etc.] and A mixture of two or more of these may be mentioned.

Aliphatic dicarboxylic acids include C4-20, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid. Can be mentioned.
Aromatic (aliphatic) dicarboxylic acids include C8-20, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, diphenoxy Examples thereof include alkali metal (sodium, potassium, etc.) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Examples of the alicyclic dicarboxylic acid include C7-14, such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and the like.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride, and examples of lower (C1-4) alkyl esters include those of the above dicarboxylic acids. Lower alkyl esters such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate.
Examples of the diamine include C6-12, such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.

Two or more of those exemplified as the amide-forming monomer may be used in combination.
Of these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferred from the viewpoint of antistatic properties.

The polyamide (m) is obtained by using one or more C4-20 dicarboxylic acids as molecular weight regulators, and in the presence thereof, ring-opening polymerization or polycondensation of the amide-forming monomer by a conventional method.
Examples of the C4-20 dicarboxylic acid include those exemplified in the above (3). Among these, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and 3-sulfoisophthalic acid are preferable from the viewpoint of antistatic properties. Alkali metal salts are preferred, with adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate being more preferred.

  The amount of the molecular weight modifier used is preferably 2 to 80% by weight and more preferably 4 to 75% by weight from the viewpoint of antistatic properties and heat resistance based on the total weight of the amide-forming monomer and the molecular weight modifier. .

  Mn of the polyamide (m) is preferably 200 to 5,000, more preferably 500 to 3,000, from the viewpoint of reactivity and the heat resistance of the obtained (A1).

Examples of the bisphenol compound constituting the AO adduct of the bisphenol compound include C12-20, such as bisphenol A, -F, and -S. Of these, bisphenol A is preferred from the viewpoint of the dispersibility of (A1) with respect to the thermoplastic resin (B) described later.
Examples of the polyalkylene glycol include AO adducts having the diol (a01) as an initiator and polyoxyalkylene having a terminal hydroxyl group.

  As AO to be added to the bisphenol compound or AO constituting the polyalkylene glycol, C2-12, for example, EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, THF, C5-12 epoxides of α-olefins, styrene oxide and epihalohydrins (eg epichlorohydrin and epibromohydrin) and mixtures of two or more thereof. Of these, EO is preferable from the viewpoint of antistatic properties.

The Mn of the AO adduct of the bisphenol compound is 300 to 5,000, preferably 400 to 4,000, more preferably 500 to 3,000 from the viewpoints of heat resistance and antistatic properties.
The Mn of the polyalkylene glycol is preferably 150 to 20,000, more preferably 300 to 15,000, and particularly preferably 1,000 to 8,000 from the same viewpoint as described above.

Among the polyethers (1a) in (A1), preferred are AO adducts (Mn 300 to 5,000) of the above bisphenol compounds and / or polyethers composed of polyalkylene glycol, and the mixture (I) or Used in the form of (II).
As the form of the mixture (I), EO adducts of bisphenol compounds having different Mn, EO adducts of bisphenol compounds-polyethylene glycol (hereinafter abbreviated as PEG), EO adducts of bisphenol compounds-EO / THF random Examples include combinations of copolymers (EO / THF weight ratio = 20/80 to 60/40).
Among these, from the viewpoint of antistatic properties, a combination of an EO adduct of a bisphenol compound-PEG and an EO adduct of a bisphenol compound-EO / THF random copolymer are preferable.

  Examples of the form of the mixture (II) include a combination of PEG-polytetramethylene glycol (hereinafter abbreviated as PTMG), a combination of PEG-polypropylene glycol (hereinafter abbreviated as PPG), and the like. Among these, the combination of PEG-PTMG is preferable from the viewpoint of antistatic properties.

  The proportion of (1a) based on the total weight of the polyamide (m) and the polyether (1a) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (A1). It is.

Specific examples of the production method of the polyetheresteramide (A1) include the following production methods (1) and (2), but are not particularly limited.
Production Method (1): An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted to form (m), to which (1a) is added, at a high temperature (160 to 270 ° C.) under reduced pressure (0. 03 to 3 kPa).
Production method (2): An amide-forming monomer and dicarboxylic acid (molecular weight modifier) and (1a) are simultaneously charged into a reaction vessel, and pressurized (0 to 270 ° C.) in the presence or absence of water at a high temperature (160 to 270 ° C.). A method of producing an intermediate (m) by reacting, and then performing a polymerization reaction with (1a) under reduced pressure (0.03 to 3 kPa).
Of the above production methods, production method (1) is preferred from the viewpoint of reaction control.

As a production method of (A1), in addition to the above, a method may be used in which the terminal hydroxyl group in (1a) is substituted with an amino group or a carboxyl group and reacted with a polyamide having a carboxyl group or an amino group at the terminal.
As a method of substituting the terminal hydroxyl group of (1a) with an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group to form an amino group [for example, (1a) and acrylonitrile And a method of hydrogenating the obtained cyanoethylated product].
Examples of the method of substituting the terminal hydroxyl group of (1a) with a carboxyl group include a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (1a) with chromic acid] and the like.

In the above polymerization reaction, a commonly used known esterification catalyst is used. Examples of the catalyst include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), metal acetate catalysts (zinc acetate, And zirconyl acetate).
The amount of the catalyst used is preferably 0.1 to 5% based on the total weight of (m) and (1a), and more preferably 0.2 to 3% from the viewpoint of reactivity and resin physical properties.

Reduced viscosity of (A1) [η _SP / C, C = 0.5 wt% (m-cresol solution, 25 ° C.), value measured using an Ubbelohde 1A viscometer, unit is dl / g, and so on. ] Is preferably 0.5 to 4, more preferably 0.6 to 3, from the viewpoint of the heat resistance of (A1) and the moldability of the resin composition. In the following, the reduced viscosity is indicated only by a numerical value.

As the block polymer (A2), in the block polymer described in WO00 / 47652, the hydrophilic polymer constituting the block polymer is a polyether (2a), and the polyether (a) in the present invention What is included. Among these, the polyolefin (b) block and the polyether (2a) block are preferably selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond from the viewpoint of antistatic properties. It is a block polymer having a structure in which it is alternately and alternately bonded through at least one kind of bond.
As the block of the polyolefin (b), polyolefins having carbonyl groups (preferably carboxyl groups), hydroxyl groups or amino groups at both ends of the polymer (b1, b2, and b3, respectively) can be used.

(B1) is preferably a carbonyl at both ends of a polyolefin (b0) having a polyolefin whose both ends can be modified as a main component (content 50% or more, more preferably 75% or more, particularly preferably 80 to 100%). And those having a group introduced therein.
As (b2), those in which hydroxyl groups are introduced at both ends of (b0) are used.
As (b3), those having amino groups introduced at both ends of (b0) are used.

  (B0) 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, but the main component is a polyolefin that can be modified at both ends. Those are preferred.

  (B0) is a polyolefin obtained by (co) polymerization (meaning polymerization or copolymerization; the same shall apply hereinafter) of one or a mixture of two or more C2-30 olefins [obtained by polymerization method] In addition, low molecular weight polyolefins [obtained by thermal degradation method] obtained by thermal degradation method of high molecular weight polyolefin (polyolefin obtained by polymerization of C2-30 olefin) can be used.

Examples of the C2-30 olefin include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin, and C4-30 (preferably 4-18, more preferably 4-4). 8) diene and the like.
Examples of the C4-30 α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, Examples thereof include cyclopentadiene and 1,11-dodecadiene.
Among these, C2-12 olefins (ethylene, propylene, C4-12 α-olefins, butadiene, and / or isoprene, etc.) are preferable, and C2-10 olefins (ethylene, propylene, C4-10) are more preferable. Of α-olefin and / or butadiene), particularly preferably 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 a known method, 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 the radical catalyst, known ones such as di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-di-carbonate ester, azo compound, etc., and oxidized to γ-alumina carrier For example, molybdenum is attached.
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 .
Of the low molecular weight polyolefin obtained by the thermal degradation method and the low molecular weight polyolefin obtained by the polymerization method, from the viewpoint of ease of introduction of the carbonyl group which is a modifying group and availability, the thermal degradation method Low molecular weight polyolefins are preferred.

Mn of (b0) 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 double bonds in (b0) is preferably 1 to 40 per 1,000 C, more preferably 2 to 30, and particularly preferably 4 from the viewpoint of antistatic properties and mechanical properties of the molded product described later. ~ 20.

The average number of double bonds per molecule is preferably from 1.1 to 5, more preferably from 1.3 to 3, particularly preferably from 1.5 to 2.5, from the same viewpoint as above. Most preferably, it is 1.8 to 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 (b1) having carbonyl groups at both ends of the polymer, both ends of (b0) are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its C1-4 Means an alkyl ester or an anhydride thereof. The same shall apply hereinafter.) Polyolefin (b11) having a structure modified with (b11) and polyolefin (b12) having a structure obtained by secondary modification of (b11) with a lactam or aminocarboxylic acid (b0) And polyolefin (b13) having a structure obtained by oxidation or hydroformylation modification), polyolefin (b14) having a structure obtained by secondary modification of (b13) with lactam or aminocarboxylic acid, and a mixture of two or more of these.

(B11) can be obtained by modifying (b0) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride), C3-12 carboxylic acid such as monocarboxylic acid [(meth) acrylic acid, etc.], dicarboxylic acid (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, alkyl esters thereof and anhydrides thereof are preferred from the viewpoint of reactivity with (b0), and maleic acid (anhydride) and fumaric acid are more preferred, and particularly preferred. Is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably 0.5 to 40% based on the weight of the polyolefin (b0), from the viewpoint of the formation of a repeating structure and antistatic properties More preferably, it is 1 to 30%, and particularly preferably 2 to 20%.
Modification of the polyolefin (b0) with an α, β-unsaturated carboxylic acid (anhydride) can be carried out by a known method, for example, the terminal double bond of (b0) is subjected to α, It can be carried out by thermally adding (ene reaction) β-unsaturated carboxylic acid (anhydride).
As a solution method, α, β-unsaturated carboxylic acid (anhydride) is added to (b0) in the presence of a hydrocarbon solvent such as xylene and toluene, and the temperature is 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. The method of making it react is mentioned.
Examples of the melting method include a method in which (b0) 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.
Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(B12) can be obtained by secondary modification of (b11) with lactam or aminocarboxylic acid.
Lactams include C6-12 (preferably 6-8, more preferably 6) lactams such as caprolactam, enantolactam, laurolactam and undecanolactam.
As aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid, for example, amino acid (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid , Ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
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.

(B13) can be obtained by oxidizing (b0) with oxygen and / or ozone or hydroformylating with an oxo method to introduce a carbonyl group.
The introduction of the carbonyl group by oxidation can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. The introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, Macromolecules, Vol. 31, 5943 page.

(B14) can be obtained by secondary modification of (b13) with lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified in (b12), and the amounts used are also the same.

Mn of polyolefin (b1) having a carbonyl group at both ends of the polymer is preferably 800 to 25,000, more preferably 1,000 to 1,000 from the viewpoint of heat resistance and reactivity with polyether (2a). It is 20,000, and particularly preferably 2,500 to 10,000.
The acid value of (b1) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (2a), and more preferably 4 to 100. Yes, particularly preferably 5-50.

As the polyolefin (b2) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (b1) with hydroxylamine and a mixture of two or more of these can be used.
Examples of hydroxylamine that can be used for the modification include C2-10 (preferably 2-6, more preferably 2-4) hydroxylamine, and the like. For example, 2-aminoethanol, 3-aminopropanol, 1-amino- Examples include 2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.
The modification with hydroxylamine can be performed by various methods, for example, by directly reacting (b1) with hydroxylamine. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
Mn of (b2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 to 10 from the viewpoint of heat resistance and reactivity with the polyether (2a). , 000.
The hydroxyl value of (b2) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (2a). Preferably it is 5-50.

As the polyolefin (b3) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (b1) with a diamine (Q1) and a mixture of two or more of these can be used.
As the diamine (Q1) used for this modification, C2-12 (preferably 2-8, more preferably 2-6) diamines can be used, for example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine. And decamethylenediamine.
Among these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.
The modification with diamine can be carried out by a known method, for example, by reacting (b1) and diamine (Q1) directly. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and still more preferably, per residue of α, β unsaturated carboxylic acid (anhydride). 0.5 to 1.2, particularly preferably 1. When the amount of diamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
In actual production, in order to prevent polyamide (imide) formation, 2 to 1,000, more preferably 5 to 800, per residue of α, β unsaturated carboxylic acid (anhydride). Particularly preferably, 10 to 500 diamines are used, and it is preferable to remove unreacted excess diamine under reduced pressure (usually 120 ° C. to 230 ° C.).

Mn of (b3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 to 10 from the viewpoint of heat resistance and reactivity with the polyether (2a). , 000.
In addition, the amine value of (b3) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with the polyether (2a), more preferably 4 to 100, Especially preferably, it is 5-50.

Examples of the polyether (2a) constituting the block polymer (A2) include those exemplified as the polyether (a).
Among the polyether components (2a), the ones exemplified as the above (1a), terminal-modified polyethers [amino group-modified polyethers (α, ω-diaminoPEG, α, ω-diaminoPTMG, etc.), isocyanate Group-modified polyethers (isocyanate group-modified -PEG, -PPG and -bisphenol compounds EOA and the like) and the like, and the like, and are used in the form of a mixture (I) or (II) as in (1a).

  Mn of the polyether (2a) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15, from the viewpoint of heat resistance and reactivity with the polyolefin (b). 000, most preferably 1,200 to 8,000.

  The block polymer (A2) 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 (b) block and the polyether component (2a) block are included. Among these, a polymer having a repeating unit represented by the following general formula (1) is preferable from the viewpoint of antistatic properties and transparency.

In the formula (1), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 25); ^one of R ¹ and R ² is H and the other is H or methyl group; y is an integer of from 15 to 800 (preferably 20 to 500, more preferably 30 to 400); E ¹ is the residue minus the hydroxyl groups from diol (a01) or dihydric phenol (a02); a ¹ is Ethylene group or C2-4 alkylene group containing ethylene group as an essential component; m and m ′ are integers of 1 to 300 (preferably 5 to 200, more preferably 8 to 150); X and X ′ are When the group selected from the formulas (2), (3) and the corresponding (2 ′), (3 ′), that is, X is a group represented by the general formula (2), X ′ is the general formula (2 ′) In general formulas (3) and (3 ′), And a similar relationship also.

In the general formulas (2) and (3) and the corresponding formulas (2 ′) and (3 ′), R is the same as described in the above (b2) and H or C1-4 (preferably 1 or 2) R ³ is a C 1-11 (preferably 2-11, more preferably 5-11) divalent hydrocarbon group, R ⁴ 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 general formulas (4), (5) and the corresponding (4 ′), (5 ′), R ⁵ is H or C1-10 (preferably 1-8, more preferably 1-6); An alkyl group, R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H is H.

The polyether segment {(OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) is the polyether diol (a1) or poly It is a structure derived from ether diamine (a2), and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

In the general formula (1), the block polymer in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) includes (b11) and / or (b12) [ Here, (b11) is a polyolefin having a structure in which both ends of the polyolefin (b0) are modified with an α, β-unsaturated carboxylic acid (anhydride), and (b12) is a polyolefin or aminocarboxylic acid (b11). (A21), (b11) and / or (b12), and polyether diamine (a2) obtained by polymerizing a polyolefin having a structure secondary modified with an acid] and a polyether diol (a1). (A22) obtained by carrying out a polymerization reaction.
(A21) includes (A211) in which (b11) and (a1) are combined, (A212) in which (b12) and (a1) are combined, and a mixture of (A211) and (A212). Similarly, (A22) includes (A221) in which (b11) and (a2) are combined, (A222) in which (b12) and (a2) are combined, and a mixture of (A221) and (A222). included.

(A21) is a known method, for example, a method in which (a1) is added to (b11) and / or (b12) and a polymerization (polycondensation) reaction is carried out under reduced pressure, preferably at 200 to 250 ° C., or uniaxial Or it can manufacture by the method of superposing | polymerizing using a twin-screw extruder, Preferably it is 160-250 degreeC and residence time 0.1-20 minutes.
In the above polymerization reaction, known catalysts such as antimony catalyst (antimony trioxide, etc.); tin catalyst (monobutyltin oxide, etc.); titanium catalyst (tetrabutyl titanate, etc.); zirconium catalyst (tetrabutyl zirconate, etc.); organic acid Metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Of these, preferred are zirconium catalyst and zirconium organic acid salt, and more preferred is zirconyl acetate.
The amount of the catalyst used is preferably 0.001 to 5%, more preferably 0.01 to 3%, based on the total weight of (b11) and / or (b12) and (a1).

Of (A21), (A212) may be reacted with (a1) after (b11) is secondarily modified with the lactam or aminocarboxylic acid, or (b11) and the lactam or aminocarboxylic acid may be reacted. The reaction may be carried out in the presence of (a1), followed by reaction with (a1).

(A22) is the same as (A21) except that the combination of (b11) and / or (b12) and (a1) in (A21) is replaced with the combination of (b11) and / or (b12) and (a2) It can be manufactured by the method.
Of (A22), (A222) may be produced by secondarily modifying (a2) with the lactam or aminocarboxylic acid and then reacting this with (b11).

In the general formula (1), the block polymer in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) includes (b13) (when r = 1) And / or (b14) (when r ≧ 2) and (a1) are subjected to a polymerization reaction (A23) and (b13) and / or (b14) and (a2) are subjected to a polymerization reaction (A24) obtained by the above.
(A23) includes (A231) in which (b13) and (a1) are combined, (A232) in which (b14) and (a1) are combined, and a mixture of (A231) and (A232). Similarly, (A24) includes (A241) in which (b13) and (a2) are combined, (A242) in which (b14) and (a2) are combined, and a mixture of (A241) and (A242). included.
(A23) and (A24) can be produced by the same method as (A21) and (A22).

  The amount of the polyether (2a) constituting the block polymer (A2) is preferably 20 to 90%, more preferably 25 to 25% based on the total weight of (2a) and (b) from the viewpoint of antistatic properties. 80%, particularly preferably 30 to 70%.

  The Mn of the block polymer (A2) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000 from the viewpoint of antistatic properties.

In the structure (A2), the average number of repeating units (Nn) of the repeating unit of the polyolefin (b) block and the polyether (2a) block is preferably 2 to 50, more preferably from the viewpoint of antistatic properties. Is 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 (A2).
For example, in the case of (A21) having a structure in which the blocks of (b11) and (a1) are alternately and repeatedly bonded, in ¹ H-NMR analysis, 4.0 to 4.1 ppm of ester bond {—C Since the signal attributed to the proton of (C═O) —OCH ₂ —} and the signal attributed to the proton of 3.2 to 3.7 ppm oxyethylene can be observed, the ratio of these proton integral values was determined. Thus, Nn can be obtained from this ratio and Mn.

  The terminal of (A2) is derived from the carbonyl group, amino group and / or unmodified polyolefin terminal derived from (b) (polyolefin terminal without any modification, ie, alkyl group or alkenyl group), or derived from polyether (2a) Either a hydroxyl group and / or an amino group. Among these, a carbonyl group, an amino group, and a hydroxyl group are preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

Examples of the polyether amide imide (A3) include those described in JP-B-7-119342 and JP-A-06-172609, wherein the polyether (3a) constituting (A3) is the polyether (a ) Are included.
Among these, caprolactam (a31), trivalent or tetravalent aromatic polycarboxylic acid (a32) which can react with an amino group to form at least one imide ring and PEG or are preferable from the viewpoint of heat resistance. Derived from a mixture (a33) of at least 50% by weight of PEG and a polyalkylene glycol other than PEG, the content of (a33) is 30 to 85% by weight, and the reduced viscosity at 30 ° C. is 1.5 to 4 Polyether amide imide is mentioned.

The aromatic polycarboxylic acid (a32) includes a trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring and an acid anhydride thereof.
Examples of the trivalent aromatic polycarboxylic acid include C9-18, such as 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′. , 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenylether-3,3 ′, 4-tricarboxylic acid, etc., and acid anhydrides thereof Things.
Examples of the tetravalent aromatic polycarboxylic acid include C10 to 20, for example, pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, benzophenone-2,2 ′, 3,3′-tetracarboxylic acid. Examples include acids, diphenylsulfone-2,2 ′, 3,3′-tetracarboxylic acid, diphenylether-2,2 ′, 3,3′-tetracarboxylic acid, and the like, and acid anhydrides thereof.

  The (a33) includes PEG or a mixture of at least 50% by weight of PEG and a polyalkylene glycol other than PEG.

  The Mn of PEG is not particularly limited, but is preferably 500 to 5,000, more preferably 800 to 3,000, from the viewpoint of imparting antistatic properties to (A3) and production.

Examples of the polyalkylene (alkylene C3-18) glycol other than PEG include PPG, PTMG, and modified polyalkylene glycol having an Mn of 500 to 5,000.
Examples of the modified polyalkylene glycol include at least two addition polymers of C2 to 10 AO (addition form may be random or block).
Among the AO, from the viewpoint of imparting antistatic properties, EO, PO, 1,3-propylene oxide, 2-methyl-1,3-propylene oxide, 2,2-dimethyl-1,3-propylene oxide, 1,5-pentamethylene oxide and 1,6-hexamethylene oxide.

  The equivalent ratio in the reaction of (a32) and (a33) is preferably 0.9 / 1 to 1.1 / 1, and more preferably 0.95 / 1 to 1.05 from the viewpoint of the resin physical properties of the molded product described later. / 1 mol.

The content of polyamideimide constituting (A3) is preferably 15 to 70% by weight, more preferably 30 to 65% by weight, from the viewpoint of imparting antistatic properties to (A3) and the water resistance of the molded product described later. .
Moreover, Mn of the polyamide-imide part in (A3) is preferably 500 to 3,000, more preferably 800 to 2,000 from the viewpoint of the heat resistance of (A3) and the mechanical strength of the molded product described later. .

Although the following method is mentioned as a manufacturing method of (A3), It does not specifically limit. That is, (a31), (a32) and (a33) are ratios in which the equivalent ratio of (a32) and (a33) is preferably 0.9 to 1.1 (more preferably 0.95 to 1.05). From the viewpoint of antistatic properties, (a33) is preferably 30 to 85% by weight, more preferably 35 to 70% by weight, based on the total weight of (a31), (a32) and (a33). This is a method of polycondensation at 150 to 300 ° C., more preferably 180 to 280 ° C. while keeping the water content of the polymer to be mixed and kept at 0.1 to 1% by weight.
In the polycondensation, the reaction temperature can be raised stepwise. At this time, some caprolactam remains unreacted, but it is desirable to remove it from the reaction mixture by distilling it off under reduced pressure from the viewpoint of the resin physical properties of the molded product described later. The reaction mixture after removing unreacted caprolactam is further polymerized by polymerizing at 200 to 300 ° C. (more preferably 230 to 280 ° C.) under reduced pressure (0.03 to 3 kPa) as necessary. It can be made into a polymer.

  The reduced viscosity of (A3) is preferably 1.5 to 4, more preferably 1.7 to 3.5 from the viewpoint of moldability of the resin composition.

As the epihalohydrin / AO copolymer (A4), for example, among those described in JP-B-7-84564, those in which the polyether (4a) constituting (A4) is included in the polyether (a) in the present invention are included. Can be mentioned.
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin, and epichlorohydrin is preferable from the viewpoint of reactivity and cost.
AO includes C2-4, such as EO, PO, and THF.
(A4) is a copolymer of epihalohydrin and a comonomer composed of one or more selected from 1,2-epoxide monomers [especially alkyl (C2-4) glycidyl ether] and AO (especially EO and PO). Mergers are also included.
The weight ratio of epihalohydrin to AO is usually 5/95 to 95/5, and preferably 10/90 to 60/40 from the viewpoint of imparting antistatic properties. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.
Among (A4), a copolymer of epichlorohydrin / EO (weight ratio 50/50) is more preferable from the viewpoint of imparting resin physical properties and antistatic properties.

In the production of (A4), a known catalyst such as an organoaluminum compound [triethylaluminum, etc.], or a catalyst obtained by reacting water with an organoaluminum compound in order to improve polymerizability is used for bulk polymerization or solution polymerization. Easy to manufacture. The molar ratio of water to the organoaluminum compound (water / organoaluminum compound) is usually 0.1 / 1 to 1/1, preferably 0.3 / 1 to 0.7 / 1, from the viewpoint of polymerizability. .
Mn of (A4) is preferably from 30,000 to 100,000, more preferably from 60,000 to 90,000, from the viewpoints of resin physical properties and moldability.

As the polyether ester (A5), for example, among those having a polyoxyethylene chain in the description of JP-B-58-19696, the polyether (5a) constituting (A5) is the polyether (a ) Are included.
(A5) is a polyester having a segment comprising a polyether diol or a copolyether diol. For example, (a32) and (a33) exemplified as the constituent components of the polyether ester amide (A1) or the polyether amide imide (A3). And a polycondensation reaction of one or more of the dicarboxylic acids exemplified as the constituent of (A1) or one or more of these ester-forming derivatives [lower (C1-4) alkyl esters, acid anhydrides, etc.] Alternatively, it can be obtained by an ester exchange reaction between the diol component and polyethylene terephthalate, polybutylene terephthalate, or the like.
The polyether segment content of (A5) is preferably 30 to 70%, more preferably 40 to 60% from the viewpoint of imparting antistatic properties to (A5) and moldability of the resin composition, and the melting point of (A5) [Measurement is DSC method] is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100%, more preferably 10 to 100%.

As the methoxypolyethylene glycol (meth) acrylate copolymer (A6), methoxypolyethylene glycol (Mn is preferably 250 to 4,950, more preferably 750 to 2,950) (meth) acrylate and a vinyl monomer described later. Among the copolymers, the polyether (6a) constituting (A6) is included in the polyether (a) in the present invention.
Mn of methoxypolyethylene glycol (meth) acrylate is preferably 300 to 5,000, more preferably 800 to 3,000, from the viewpoint of antistatic properties.
Preferred monomers to be copolymerized are (meth) acrylic acid, alkyl (C1-20) (meth) acrylate [C4-24, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate]. is there.
Mn of (A6) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of physical properties of the resin, and the methoxypolyethylene glycol (meth) acrylate unit and vinyl monomer in (A6) The weight ratio of the units is preferably 20/80 to 80/20, more preferably 30/70 to 60/40 from the viewpoint of antistatic properties.

The polyether group-containing ethylene / vinyl acetate copolymer (A7) is obtained by hydrolyzing an ethylene / vinyl acetate copolymer to give an ethylene / vinyl alcohol copolymer and adding EO (A7) Are included in the polyether (a) in the present invention.
The weight ratio of the ethylene unit and vinyl acetate unit in (A7) is preferably 20/80 to 80/20, more preferably 30/70 to 60/40, from the viewpoint of antistatic properties, and hydrolysis of the vinyl acetate unit. The rate [vinyl acetate unit before hydrolysis / vinyl alcohol unit after hydrolysis] (mol%) is preferably 30 to 100 mol%, more preferably 40 to 80 mol%, from the viewpoint of antistatic properties. The number of moles of EO added per vinyl alcohol unit is preferably 5 to 30, more preferably 10 to 20, from the viewpoint of antistatic properties.
Mn of (A7) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of resin physical properties.

[Crystallinity of oxyethylene group moiety]
The degree of crystallinity of the oxyethylene group portion measured by a differential scanning calorimetry (DSC) method in the copolymer (A) in the present invention is 0 to 30%, preferably 0 to 26%. When the crystallinity exceeds 30%, the antistatic property deteriorates. The crystallinity can be measured by the following method.
<Method for measuring crystallinity>
The degree of crystallinity can be obtained from the following equation [New Journal of
Chemistry, 2005, vol. 29, p. 1454].

Crystallinity (%) = [ΔHm / [Oxyethylene in antistatic agent or antistatic resin composition]
Group content (%)]] × 10,000 / ΔHm *

In the formula, ΔHm is the melting enthalpy derived from the oxyethylene group in the antistatic agent or antistatic resin fat composition (unit is J / g, the same applies hereinafter), ΔHm * is the melting enthalpy of PEG [reference (above) Value 213.7 J / g].
Here, the melting enthalpy indicates only the melting enthalpy at that temperature when the melting peak temperature is one point, and indicates the sum of the melting enthalpies at each temperature when there are a plurality of melting peak temperatures.

As a differential scanning calorimeter (DSC) used for the measurement, for example, DSC2910 [trade name, manufactured by T.A. Instruments Co., Ltd.] can be mentioned. According to the measurement method, it can be determined based on the melting enthalpy measured under the following conditions.
[Measurement condition]
After the sample was conditioned for 24 hours or more in the standard temperature state grade 2 and standard humidity state grade 2 described in JIS K 7100, about 5 mg was weighed, heated to 250 ° C. at a heating rate of 10 ° C. per minute, and held for 10 minutes. Cool to −50 ° C. at a cooling rate of 10 ° C. per minute. From the obtained DSC curve, the heat of transition (melting enthalpy) by heating is determined.

  Specifically, the thermoplastic resin (B) in the present invention is a vinyl resin [polyolefin resin (B1) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.] , Polyacrylic resin (B2) [for example, polymethyl methacrylate, etc.], polystyrene resin (B3) [vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic acid ester, (meth) Copolymers having at least one selected from the group consisting of acrylonitrile and butadiene as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methacryl Methyl acid / butadiene / styre Copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin), etc.]]; polyester resin (B4) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene Adipate, etc.]; polyamide resin (B5) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.]; polycarbonate resin (B6) [ For example, polycarbonate, polycarbonate / ABS resin alloy, etc.]; polyacetal resin (B7) and a mixture of two or more thereof.

  Of these, vinyl resins [(B1) to (B3)] and polyamide resin (B5) are preferable from the viewpoint of ease of dispersion of (A) into (B), and (B1) and (B3).

  The vinyl resins [(B1) to (B3)] are obtained by (co) polymerizing the following vinyl monomers by a known polymerization method (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.).

  Examples of vinyl monomers include unsaturated hydrocarbons (aliphatic hydrocarbons, aromatic ring-containing hydrocarbons, alicyclic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- or dicarboxylic acids and their derivatives, and carboxylic acids of unsaturated alcohols. Examples include acid esters, alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations (random and / or block) of two or more thereof.

  Aliphatic hydrocarbons include C2-30 olefins [ethylene, propylene, C4-30 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1 -Dodecene etc.), etc.], C4-30 dienes [alkadiene (butadiene, isoprene etc.), cycloalkadiene (cyclopentadiene etc.) etc.] and the like.

  Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and derivatives thereof, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene, etc.), α-alkyl (C1-10) styrene ( α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).

Acrylic monomers include those having C3-30, such as (meth) acrylic acid and its derivatives.
Examples of (meth) acrylic acid derivatives include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.], mono- and di-alkyl (C1). -4) Aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylonitrile, and (meth) acrylamide.

  Other unsaturated mono- and dicarboxylic acids include C2-30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid and itacon. Examples thereof include C5-30, such as mono- and dialkyl (C1-20) esters, acid anhydrides (maleic anhydride, etc.) and acid imides (maleic imide, etc.).

Examples of carboxylic acid esters of unsaturated alcohols include carboxylic acids (C2-4, such as acetic acid, propionic acid) esters (vinyl acetate, etc.) of unsaturated alcohols [C2-6, such as vinyl alcohol, (meth) allyl alcohol]. It is done.
Examples of the alkyl ether of the unsaturated alcohol include alkyl (C1-20) ethers of the above unsaturated alcohol (such as methyl vinyl ether and ethyl vinyl ether).
Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (B1) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [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 ] Etc. are mentioned.
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (B1) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of imparting resin physical properties and antistatic properties. MFR of (B1) is JIS
According to K6758 (in the case of polypropylene; 230 ° C., load 2.16 kgf, in the case of polyethylene; 190 ° C., load 2.16 kgf).

  Examples of the polyacrylic resin (B2) include one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.]). Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (B1) are excluded] are included.

  The MFR of (B2) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. The MFR of (B2) is measured in accordance with JIS K7210 (1994) [230 ° C., load 1.2 kgf for polyacrylic resin (B3)].

As the polystyrene resin (B3), vinyl group-containing aromatic hydrocarbons alone or vinyl group-containing aromatic hydrocarbons and at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of the vinyl group-containing aromatic hydrocarbon include C8-30 styrene and derivatives thereof, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene etc.), α-alkyl (C1-10). Examples include styrene (α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).
Specific examples of (B3) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin) [Copolymerization ratio (weight ratio) = (48-70) / (0-5) / (2-20) / (25-50)], and the like.

  The MFR of (B3) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B3) is measured according to JIS K6871 (1994) (in the case of polystyrene resin, 230 ° C., load 1.2 kgf).

  Examples of the polyester resin (B4) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (B4) is preferably 0.1 to 4, more preferably 0.2 to 3.5, and particularly preferably 0.3 to 3 from the viewpoints of resin physical properties and antistatic properties. Here, [η] is a value (unit: dl / g) measured with an Ubbelohde 1A viscometer at 25 ° C. with respect to a 0.5 wt% orthochlorophenol solution of the polymer, and so on. Note that [η] is indicated only by a numerical value in the following.

  As the polyamide resin (B5), a lactam ring-opening polymer (B51), a dehydration polycondensation product of diamine and dicarboxylic acid (B52), a self-polycondensation product of aminocarboxylic acid (B53), and a poly (condensation) combination thereof Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (B51) include those exemplified above (C6-12, such as caprolactam, enantolactam, laurolactam, undecanolactam), and (B51) includes nylon 4, nylon 5, nylon 6, Nylon 8, nylon 12, etc. are mentioned.
Examples of the diamine and dicarboxylic acid in (B52) include those exemplified above. Examples of (B52) include nylon 66 by condensation polymerization of hexanemethylenediamine and adipic acid, and nylon by polycondensation of hexamethylenediamine and sebacic acid. 610 etc. are mentioned.
Examples of the aminocarboxylic acid in (B53) include those exemplified above. Examples of (B53) include nylon 7 by polycondensation of aminoenanthate and nylon 11,12-amino by polycondensation of ω-aminoundecanoic acid. Examples thereof include nylon 12 by polycondensation of dodecanoic acid.

In the production of (B5), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acids and / or diamines exemplified above.
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate.
Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

  The MFR of (B5) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B5) is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

As the polycarbonate resin (B6), bisphenol (C12-20, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, etc.) type polycarbonate, for example, the above bisphenol and phosgene or carbonic acid diester And a condensate thereof.
Examples of the bisphenol include C12-20, such as bisphenol A, bisphenol F, bisphenol S, and 4,4′-dihydroxydiphenyl-2,2-butane. Among these, bisphenol A is more preferable from the viewpoint of dispersibility. is there.
The MFR of (B6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B6) is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (B7) include a homopolymer of formaldehyde or trioxane (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [said AO (EO, PO, dioxolane, etc.) (polyoxymethylene / Polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer, etc.] and the like.
The MFR of (B7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B7) is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (B7) is preferably 0.1 to 4, more preferably 0.2 to 3.5, and particularly preferably 0.3 to 3 from the viewpoints of resin physical properties and antistatic properties.

  The antistatic resin composition of the present invention is produced by melt-mixing (A) and (B) so that (A) is contained in (B), and the dispersed phase comprising (A) and (B) The number average particle diameter, number average minor diameter, or number average thickness of the dispersed phase is preferably 0.01 to 1 μm. A method of melt mixing will be described later. The content of (A) in (B) can be variously changed according to the required performance, but from the viewpoint of providing sufficient antistatic properties and mechanical properties, the total of (A) and (B) is preferable. Based on weight, it is preferably 1 to 40%, and more preferably 1.5 to 30%.

  In the present invention, for the purpose of improving the compatibility between (A) and (B), at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group. You may contain the modified vinyl copolymer (C) which has. The amount of (C) used is preferably 0.1 to 15%, more preferably 1 to 10%, based on the total weight of (A) and (B), from the viewpoint of resin physical properties.

  Examples of the vinyl monomer (c1) constituting the above (C) include vinyl monomers having a functional group reactive or compatible with the carboxyl group, hydroxyl group and / or amide group present in (A). For example, a vinyl monomer having at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyoxyalkylene group and derivatives thereof described in JP-A-3-258850 is exemplified. be able to.

Examples of vinyl monomers having a carboxyl group (including an anhydride group) include monocarboxylic acids [C3-15, such as (meth) acrylic acid, 4-vinyl-benzoic acid], dicarboxylic acids [C4-15, such as ( Anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid], dicarboxylic acid monoester [monoalkyl (C1-8 or more, eg methyl, ethyl, butyl, octyl) ester of the above dicarboxylic acid, eg malee Acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester, etc.].
Specific examples of the vinyl monomer having an epoxy group include C5-12, such as glycidyl (meth) acrylate and glycidyl itaconate.
Specific examples of the vinyl monomer having an amino group include those of C5 to 16, such as alkyl ester derivatives of (meth) acrylic acid [aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, (meth ) Methylaminoethyl acrylate, ethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, etc.], vinylamine derivatives [N-vinyldiethylamine, N-acetylvinylamine, etc. ], Amino styrene [p-amino styrene etc.] etc. are mentioned.
Examples of vinyl monomers having a polyoxyalkylene group include (meth) acrylates [polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth)] of polyalkylene glycol (Mn 150 to 3,000). Acrylate etc.] and the like.
Among these vinyl monomers, a vinyl monomer having a carboxyl group, an epoxy group, an amino group, a hydroxyl group and / or a polyoxyalkylene group is preferable from the viewpoint of reactivity or affinity with (A), More preferred are vinyl monomers having a carboxyl group, an epoxy group and / or an amino group, and particularly preferred are vinyl monomers having an epoxy group.

(C) is obtained by using the vinyl monomer (c1) as an essential constituent unit and, if necessary, copolymerizing with another vinyl monomer. There is no restriction | limiting in particular as another vinyl monomer (c2), A thing other than (c1) is mentioned.
As (c2), aromatic vinyl monomer [C8-20, eg styrene], vinyl cyanide [C3-6, eg (meth) acrylonitrile], (meth) acrylic acid ester [C4-30, eg methacrylic] Acid methyl], maleimide [C5-30, such as N-methylmaleimide], olefin [C2-12, such as ethylene, propylene] and halogen-containing vinyl monomer (C2-12, such as vinyl chloride).
In addition, (C) includes those obtained by post-modifying the above-mentioned (c1) by addition reaction with heat-degraded polyolefin.

  (C2) can be selected according to the type of the thermoplastic resin (B) in the present invention. For example, when (B) is a polystyrene resin (B3), the compatibility between (A) and (B3) is improved. For the purpose of illustration, it is preferable to copolymerize a vinyl monomer (such as styrene) as a component of (B3), and when (B) is an acrylonitrile / butadiene / styrene copolymer (ABS), It is preferable to copolymerize vinyl cyanide such as (meth) acrylonitrile and / or aromatic vinyl monomers such as styrene.

The method for producing (C) is a commonly used method, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method in the presence of a known polymerization initiator. A solution polymerization method is preferable from the viewpoint of ease of process.
The Mn of (C) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 5,000 to 100,000, from the viewpoints of dispersibility in the resin composition and resin physical properties.

The method of adding (C) is not particularly limited, but from the viewpoint of effective dispersion in the resin composition of (C), a method of dispersing in (A) in advance is preferable. Further preferred is a method in which (C) is previously added and dispersed during the production of (A) [in the raw material of (A), during the production of (A) and / or after the production of (A)].

In addition, the antistatic resin composition of the present invention may contain an antistatic agent (D) other than (A) as necessary for the purpose of further improving the antistatic property.
(D) includes surfactant (D1) [anionic surfactant (D11), cationic surfactant (D12), nonionic surfactant (D13), amphoteric surfactant (D14), etc.] and (D1) Examples include salts (D2) other than the salt in them.

Examples of the anionic surfactant (D11) include carboxylate, sulfate ester salt, sulfonate salt and phosphate ester salt.
The cation constituting (D11) is not particularly limited as long as it forms a salt, and usually includes alkali metal, alkaline earth metal, ammonium and the like.

  Examples of the carboxylate include salts of C8-20 higher fatty acids (octanoic acid, lauric acid, stearic acid, oleic acid, eicosanoic acid, etc.).

  The sulfate ester salts include sulfate ester salts of C8-20 higher alcohols (octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, eicosyl alcohol, etc.) and higher alkyl ethers [EO of the above higher alcohols (1 to 50 mol). ) Additives] sulfate salts, funnel oil, castor oil, sulfated oils (sulfated cow oil, sulfated peanut oil, sulfated macquarium whale oil, etc.), sulfated fatty acid esters (sulfated) Butyl oleate, sulfated ricinoleate butyl, etc.) and C8-20 sulfated olefin salts.

Examples of sulfonates include alkylbenzene sulfonates having C8-20 alkyl (octyl, lauryl, octadecyl, eicosyl, etc.) groups, C8-20 alkyl (above) sulfonates, and C10-20 (alkyl). Naphthalene (di) sulfonate (1-naphthalenesulfonate, 1,4-naphthalenedisulfonate, 2-methyl-1-naphthalenesulfonate, 2-methyl-1,4-naphthalenedisulfonate, etc.), Α8-olefin sulfonate of C8-20, Igepon T-type sulfonate and sulfosuccinate dialkyl ester having C8-20 alkyl group (such as di-2-ethylhexyl sulfosuccinate sodium salt), polyvinyl sulfonate (polystyrene) Sulfonic acid salts and the like).
Examples of phosphoric acid ester salts include mono- and di-ester salts of C8-20 higher alcohols (above).

These anionic surfactants (D11) may be one kind or a mixture of two or more kinds.
Of these, higher fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates and mixtures thereof are preferable from the viewpoint of antistatic properties, and stearates, dodecylbenzene sulfonates, lauryl sulfonates are more preferable. And mixtures thereof, particularly preferred are sodium stearate, sodium dodecylbenzene sulfonate, sodium lauryl sulfonate and mixtures thereof.

  Examples of the cationic surfactant (D12) include quaternary ammonium salts and / or phosphonium salts such as compounds represented by the following general formula (6).

Wherein J is a nitrogen atom or phosphorus atom (preferably a nitrogen atom); R ⁷ and R ¹⁰ are C 1-20 alkyl groups or C 6-20 (substituted) phenyl groups; R ⁸ and R ⁹ are amides May have a bond, an imide bond, an ester bond, an ether bond or a urea bond, and R ⁸ and R ⁹ may be bonded to each other to form a ring or a C1-20 alkylene group or (substituted) ) Phenylene group; M- is an anion; v is an integer of 1 to 10 (preferably 1 to 6).

As the anion constituting (D12), the heat loss start temperature in the air of (D12) [The heat loss start temperature is the same as that of JIS K7120 (1987). The value measured according to the method for analyzing the TG curve described in the item] can be used at 200 ° C. or higher, a conjugate base of a super strong acid [Hammett acidity function (−H ⁰ ) of at least 12], and others Of the anion.
When R ⁷ , R ⁸ , R ⁹ and R ¹⁰ do not have β hydrogen (for example, tetramethylammonium, trimethylbenzylammonium), Hofmann decomposition cannot occur, so that the conjugate base of super strong acid and other anions However, when R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have β hydrogen (for example, trimethylethylammonium, didecyldimethylammonium), a conjugate base of a super strong acid is preferable.

  Examples of anions other than the conjugate base of super strong acid include halogen (fluorine, chlorine, bromine, etc.) ions, p-toluenesulfonic acid ions, undecafluoropentanesulfonic acid ions, and the like.

Super strong acids include those derived from proton acids and combinations of proton acids and Lewis acids.
Examples of the protonic acid as the super strong acid include perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, and tridecafluorohexanesulfonic acid.

  Examples of the protonic acid used in combination with Lewis acid include hydrogen halide (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfone. Examples include acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid. Of these, hydrogen fluoride is preferred from the viewpoint of antistatic properties.

Examples of Lewis acids include fluorides of group IIIA elements (boron, tantalum, etc.) (boron trifluoride, tantalum pentafluoride, etc.) and fluorides of group VA elements (phosphorus, antimony, arsenic, etc.) (phosphorus pentafluoride). , Antimony pentafluoride, arsenic pentafluoride, etc.). Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of antistatic properties.
A combination of a protonic acid and a Lewis acid is arbitrary, but as a super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluorosulfone Examples thereof include acid, tetrafluoroboric acid, hexafluorophosphoric acid, and chlorotrifluoroboric acid. These may be used alone or as a mixture of two or more.

  Among the anions constituting (D12), preferred from the viewpoint of antistatic properties is a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid conjugate base consisting of a combination of a proton acid and a Lewis acid), Further preferred is a super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride among Lewis acids.

Specific examples of quaternary ammonium salts in (D12) are: (1) salts with anions other than conjugate bases of super strong acids, and (2) super strong acids (protonic acids, combinations of proton acids and Lewis acids). Examples are divided into salts with conjugate bases.
(1) Salts of super strong acids with anions other than conjugate bases Quaternary ammonium such as tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, trimethyldodecylammonium, didecyldimethylammonium and trimethyl-2-ethylhexylammonium Examples include salts in combination with anions other than strong acid conjugate bases, such as fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid, and the like.

(2-1) Salt of super strong acid (protonic acid) with conjugate base Above quaternary ammonium and super strong acid (protonic acid) conjugate base, such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethane Examples thereof include salts obtained by combining sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid and tridecafluorohexanesulfonic acid.

(2-2) Salt of super strong acid (combination of proton acid and Lewis acid) with conjugate base Conjugate base of quaternary ammonium and super strong acid (combination of proton acid and Lewis acid), for example, tetrafluoroboric acid , Salts of hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorotantalum sulfonic acid and the like.

Of (D12), specific examples of phosphonium salts include (3) a salt of an anion other than a conjugate base of a super strong acid, and (4) a conjugate base of a super strong acid (a combination of a proton acid, a proton acid and a Lewis acid). Examples are divided into salts.
(3) A salt of a super strong acid with an anion other than a conjugate base. Examples include salts in combination with anions other than bases, such as fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid, and the like.

(4-1) Salt of super strong acid (protonic acid) with conjugate base The above phosphonium and super strong acid (protonic acid) conjugate base, such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethanesulfonic acid, Examples thereof include salts combined with pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, tridecafluorohexanesulfonic acid, and the like.

(4-2) Salt of super strong acid (combination of proton acid and Lewis acid) with conjugate base The conjugate base of phosphonium and super strong acid (combination of proton acid and Lewis acid) such as tetrafluoroboric acid, hexafluoro Examples thereof include salts obtained by combining phosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, and hexafluorotantalum sulfonic acid.

Of the above (1) to (4), from the viewpoint of antistatic properties, a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid conjugate base comprising a combination of a proton acid and a Lewis acid) is preferred. More preferably, it has a super strong acid composed of a protonic acid and a super strong acid conjugate base composed of boron trifluoride and / or phosphorus pentafluoride among the protonic acid and Lewis acid.
These may be used singly or as a mixture of two or more thereof, or may be a mixture of an anion other than a super strong acid conjugate base and a super strong acid conjugate base. In the case of a mixture of an anion other than a conjugate base of a super strong acid and a conjugate base of a super strong acid, the ratio (weight ratio) is preferably 95/5 to 5/95, more preferably 70/30 to from the viewpoint of antistatic properties. 30/70.

  Nonionic surfactants (D13) include polyethylene glycol type [EO (1-50 mol) adduct of higher alcohol (same as above), EO (1-30 mol of higher fatty acid (same as above)). ) Adduct, EO (1-50 mol) adduct of higher alkylamine (C8-18, such as 1-octylamine, 1-dodecylamine, etc.), EO of polypropylene glycol (Mn 1,000-3,000) (5 -150 mol) adducts, etc.]; polyhydric alcohol type [polyethylene oxide (degree of polymerization n = 3-300), fatty acid of glycerin (C4-30, such as caproic acid, octylic acid, lauric acid, stearic acid, oleic acid, etc. ) Esters, pentaerythritol fatty acids (above) esters, sorbitol or sorbitan fatty acids (above) Esters, polyhydric alcohols (C3-12, such as glycerin, sorbitan, etc.) alkyl (C1-30) ether, fatty acid alkanolamines (C2-20) (as mentioned above) amide], and the like.

  Examples of the amphoteric surfactant (D14) include amino acid type [higher alkyl (C8-18) aminopropionate and the like], betaine type [higher alkyl (C8-18) dimethylbetaine, higher alkyl (C8-18) dihydroxyethyl betaine. Etc.]. These may be used alone or in combination of two or more.

Examples of other salts (D2) include salts of alkali metals (lithium, sodium, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.) and protonic acids.
Examples of the protonic acid include those exemplified as those used in combination with the Lewis acid.

Specific examples of (D2) include fluoride (lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, etc.), chloride (lithium chloride, sodium chloride, potassium chloride, magnesium chloride, chloride). Calcium), bromide (lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc.), iodide (lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide) Etc.), perchlorates (lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, calcium perchlorate, etc.), fluorinated sulfonates (lithium fluorosulfonate, sodium fluorosulfonate) , Potassium fluorosulfonate, magnesium fluorosulfonate, full Calcium sulfonate, etc.), methanesulfonate (lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, etc.), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, Sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, sodium pentafluoroethanesulfonate, pentafluoroethane) Potassium sulfonate, magnesium pentafluoroethanesulfonate, calcium pentafluoroethanesulfonate ), Nonafluorobutanesulfonate (lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, etc.), undecafluoropentane Sulfonates (lithium undecafluoropentanesulfonate, sodium undecafluoropentanesulfonate, potassium undecafluoropentanesulfonate, magnesium undecafluoropentanesulfonate, calcium undecafluoropentanesulfonate), tridecafluorohexane Sulfonate (lithium tridecafluorohexanesulfonate, sodium tridecafluorohexanesulfonate, tridecafluorohexanesulfonate Potassium acetate, magnesium tridecafluorohexanesulfonate, calcium tridecafluorohexanesulfonate, etc.).
Of these, chlorides and perchlorates are preferable from the viewpoint of antistatic properties, and lithium chloride, potassium chloride, lithium perchlorate, potassium perchlorate and sodium perchlorate are more preferable.

The amount of the other antistatic agent (D) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, based on the total weight of (A) and (B), from the viewpoint of resin physical properties. %.
The method for adding (D) is not particularly limited, but from the viewpoint of effective dispersion in the resin composition of (D), a method of dispersing in (A) in advance is preferable. Further preferred is a method in which (D) is added and dispersed in advance during the production of (A) [in the raw material of (A), during the production of (A) and / or after the production of (A)].

To the antistatic resin composition of the present invention, other resin additives (E) can be added as necessary within a range not impairing the effects of the present invention.
The (E) may be added after the resin composition comprising (A) and (B) is mixed, or may be previously contained in (A).
(E) includes colorant (E1), filler (E2), nucleating agent (E3), lubricant (E4), plasticizer (E5), mold release agent (E6), antioxidant (E7), difficulty A flame retardant (E8), an ultraviolet absorber (E9), an antibacterial agent (E10), etc. are mentioned.

Examples of the colorant (E1) include pigments and dyes.
Examples of pigments include inorganic pigments (titanium oxide, aureolin, iron oxide, chromium oxide, cadmium sulfide, etc.); organic pigments (azo lake, monoazo, disazo, chelate azo, benzimidazolone, phthalocyanine, quinacridone, dioxazine Type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone type, etc.).

As dyes, azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro , Nitroso, aniline and the like.
The amount of (E1) used is preferably 5% or less, more preferably 0.1 to 3%, based on the total weight of (A) and (B).

Examples of the filler (E2) include fibrous, granular, and plate-like fillers.
Examples of the fibrous filler include glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, aramid fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, and the like. Among these, glass fibers and carbon fibers are preferable from the viewpoint of the mechanical strength of the molded product.
As granular fillers, carbon black, silica, quartz powder, glass beads, silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, zinc oxide, alumina, etc.) , Metal carbonate (calcium carbonate, magnesium carbonate, etc.), metal sulfate (calcium sulfate, barium sulfate, etc.), silicon carbide, silicon nitride, boron nitride and various metals (magnesium, silicon, aluminum, titanium, copper, silver) , Gold, etc.) and the like.
Examples of the plate-like filler include mica, glass flakes and various metal (aluminum, copper, silver, gold, etc.) foils.
These fillers may be used alone or in combination of two or more.
Of the above fillers, a fibrous filler is preferable from the viewpoint of the mechanical strength of the molded product, and a glass fiber is more preferable.
The amount of filler used is preferably 150% or less, more preferably 5 to 100%, based on the total weight of (A) and (B).

As the nucleating agent (E3), 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-tert-butylphenyl) phosphate, Examples thereof include sodium benzoate.
The amount of (E3) used is preferably 20% or less, more preferably 1 to 10%, based on the total weight of (A) and (B).

Examples of the lubricant (E4) include waxes (such as carnauba wax), higher fatty acids (as described above, such as stearic acid), higher alcohols (as described above, such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide). Is mentioned.
The amount of (E4) used is preferably 20% or less, more preferably 1 to 10%, based on the total weight of (A) and (B).

Examples of the plasticizer (E5) include aromatic carboxylic acid esters [phthalic acid esters (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid esters [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], aliphatic Dicarboxylic acid esters [di (2-ethylhexyl) adipate, adipic acid-propylene glycol-based polyester, etc.], aliphatic tricarboxylic acid esters [citric acid esters (such as triethyl citrate), etc.], phosphoric acid triesters [triphenyl phosphate, etc. ], Epoxide [epoxidized oil, epoxy fatty acid ester (epoxy butyl stearate, epoxy octyl stearate, etc.)], petroleum resin and the like.
The amount of (E5) used is preferably 20% or less, more preferably 1 to 10%, based on the total weight of (A) and (B).

As the release agent (E6), lower fatty acid (C1-4) alcohol ester (such as butyl stearate) of higher fatty acid (as described above), polyhydric alcohol ester of fatty acid (C4-30) (such as hardened castor oil), Examples include glycol esters of fatty acids (above) (such as ethylene glycol monostearate) and liquid paraffin.
The amount of (E6) used is preferably 10% or less, more preferably 0.1 to 5%, based on the total weight of (A) and (B).

Antioxidants (E7) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.], polycyclic phenol [1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-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 [trade name “Irganox 1010”, manufactured by Ciba Geigy Co., Ltd.], etc.], bisphenol [2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl) 6-t-butylphenol) etc.]; Sulfur [dilauryl-3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate , Dimyristyl-3,3′-thiodipropionate, distearyl-β, β′-thiodibutyrate, dilauryl sulfide, etc.]; Phosphorus [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-tert-butylphenylditridecyl) phosphite, cyclic neopentane Trilebis (octadecylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite], cyclic neopentanetetraylbis (2,4-di-t-) Butylphenyl) phosphite, diisodecylpentaerythritol diphosphite]; amine-based [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, phenothiazine and the like.
The amount of (E7) used is preferably 5% or less, more preferably 0.1 to 3%, based on the total weight of (A) and (B).

Examples of the flame retardant (E8) include organic flame retardants [nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) and other salts (inorganic acid salts, cyanurates, isocyanurates, etc.), etc.] ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphate ester (tri Etc.], etc.], inorganic flame retardants [antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate, etc.].
The amount of (E8) used is preferably 20% or less, more preferably 3 to 15%, based on the total weight of (A) and (B).

Examples of the ultraviolet absorber (E9) include benzotriazole-based [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxyphenyl) benzotriazole, etc.], benzophenone-based (2-hydroxy Benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), salicylic acid type (phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), acrylate type (2-ethylhexyl-2-cyano-3,3 ′, 1-diphenyl acrylate and the like).
The amount of (E9) used is preferably 5% or less, more preferably 0.1 to 3%, based on the total weight of (A) and (B).

Antibacterial agents (E10) include quaternary ammonium salts [trimethoxysilyl-propyloctadecylammonium chloride, etc.], pyridine compounds [2,3,5,6-cytochloro-4- (methylsulfonyl) -pyridine, etc.], organic Acid (ester) [benzoic acid, sorbic acid, paraoxybenzoic acid ester, etc.], halogenated phenol [2,4,6-tribromophenol sodium salt, 2,4,6-trichlorophenol sodium salt, parachlorometaxylenol, etc. ], Organic iodine [4-chlorophenyl-3-iodopropargyl formal, 5-chloro-2-methyl-4-isothiazolin-3-one, etc.].
The amount of (E10) used is preferably 3% or less, more preferably 0.05 to 1%, based on the total weight of (A) and (B).

The antistatic resin composition of the present invention is produced by melt-mixing (A) and (B) and, if necessary, (C), (D), and (E).
As a method of melt-mixing, a normal method, for example, pellets or powdery polymers are mixed with an appropriate mixer such as a Henschel mixer and then melt-kneaded (temperature 160 to 280 ° C.) with an extruder. The method of pelletizing after that is mentioned.
The kneading time is preferably 0.1 to 10 minutes, more preferably 1 to 7 minutes. If it is 0.1 minutes or longer, kneading is sufficient, and if it is 10 minutes or less, resin deterioration is unlikely to occur. The kneading temperature is preferably not lower than the melting point of (B) and not higher than 280 ° C. When the temperature is 280 ° C. or lower, resin deterioration hardly occurs. The size of the pelletized pellet is not particularly limited, but is preferably a cylindrical shape having a diameter of 1 to 5 mm and a height of 1 to 5 mm from the viewpoint of ease of handling during molding.
There are no particular restrictions on the order of addition of each component during kneading, for example, (1) (A) and (B), and, if necessary, (C) to (E) are batch blended and kneaded, and (2) a small amount (B), (A), and, if necessary, (C) to (E) after blending / kneading, the remaining (B) is blended / kneaded, and (3) (A), (C ), (D) and (E) are blended / kneaded and then (B) is blended / kneaded.
Of these, the method (2) is a method called a master batch method or a master pellet method.

Methods for molding the antistatic resin composition of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) Depending on the purpose, it can be molded by any method incorporating means such as single layer molding, multilayer molding or foam molding.
The molded product obtained from the resin composition of the present invention has excellent mechanical properties and permanent antistatic properties, as well as good paintability and printability.
Examples of the method for coating the molded product 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 paint include paints generally used for painting plastic such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
Moreover, as a method of printing on the molded product or the molded product after coating, printing methods generally used for plastic printing, for example, gravure printing, flexographic printing, screen printing, and offset printing can be mentioned. .
Examples of the printing ink include those usually used for printing plastics.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents weight percent.

Example 1
In a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, antioxidant “Irganox 1010” [manufactured by Ciba Specialty Chemicals Co., Ltd., and so on. ] 0.3 parts and 6 parts of water were charged, the inside of the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours under sealed conditions. Acid value having carboxyl groups at both ends 96 parts of 112 (1,000) polyamide (m-1) was obtained.
Next, 124 parts of EO product of bisphenol A (aE-1) (Mn3,000), EO / THF random copolymer (aE-2) (EO / THF = weight ratio 40/60, Mn3,000, and so on) 50 parts [HLB of the two mixed polyethers (a-1) is 16] and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous solution. Obtained a polymer. The polymer was taken out in the form of a strand on a belt and pelletized to obtain an antistatic agent (X-1) comprising a polyether ester amide (A-1). The volume resistivity value of (A-1) was 5 × 10 ⁷ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-1) measured by DSC was 14%.

Example 2
In Example 1, 143 parts of (aE-1) instead of 124 parts and (aE-2) of EO adduct of bisphenol A (aE-3) (Mn2,000) 38 parts were used instead of 50 parts. [An antistatic agent (X-2) comprising a polyether ester amide (A-2) was obtained in the same manner as in Example 1 except that the HLB of the two mixed polyethers (a-2) was 19). . The volume resistivity value of (A-2) was 2 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-2) measured by DSC was 26%.

Example 3
A stainless steel autoclave was charged with 87 parts of 12-aminododecanoic acid, 13 parts of adipic acid, 0.3 part of antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. 0.5 MPa) was stirred for 4 hours in a sealed state to obtain 96 parts of polyamide (m-2) having an acid value of 108 (Mn 1,000) having carboxyl groups at both ends.
Next, 132 parts of EO product of bisphenol A (aE-1), 15 parts of EO product of bisphenol A (aE-4) (Mn400) [HLB of the two mixed polyethers (a-3) is 17] Then, 0.5 part of zirconyl acetate was added, and an antistatic agent (X-3) comprising a polyetheresteramide (A-3) was obtained in the same manner as in Example 1. The volume resistivity value of (A-3) was 4 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-3) measured by DSC was 16%.

Example 4
In Example 3, 132 parts of (aE-3) were used in place of 132 parts of (aE-1), except that the HLB of the two mixed polyethers (a-4) was 17). Similarly, an antistatic agent (X-4) comprising a polyether ester amide (A-4) was obtained. The volume resistivity value of (A-4) was 1 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-4) measured by DSC was 0%.

Example 5
Ethylene obtained by a thermal degradation method [A density of 0.90 at 23 ° C., MFR 6.0 g / 10 min ethylene / propylene random copolymer (ethylene content 2%) at 410 ± 0.1 ° C.] / Propylene random copolymer (Mn 3,500, density 0.89, 7.1 double bonds per 1,000 C, average number of double bonds per molecule 1.8, both ends can be modified) Polyolefin content 90%) 95 parts, maleic anhydride 10 parts, and xylene 30 parts were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b1-1). The acid value of (b1-1) was 27.2, and Mn was 3,700.
(B1-1) 66 parts and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. in a nitrogen gas atmosphere, reacted at 200 ° C. for 3 hours under reduced pressure of 1.3 kPa or less, and acid-modified polypropylene (b1 -2) was obtained. The acid value of (b1-2) was 17.7, and Mn was 5,700.
In a stainless steel autoclave, 66 parts (b1-2), 31 parts PEG (Mn6,000) (aE-5)), 3 parts EO adduct of bisphenol A (Mn1,000) (aE-6) [the two kinds HLB of the mixed polyether (a-5) of 20], 0.3 part of an antioxidant and 0.5 part of zirconyl acetate were charged, and polymerized for 4 hours at 230 ° C. under reduced pressure of 0.13 kPa or less. A viscous polymer was obtained. The polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X-5) comprising a block polymer (A-5). The volume specific resistance value of (A-5) was 3 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-5) measured by DSC was 24%.

Example 6
In Example 5, 40 parts of the acid-modified polypropylene (b1-2) was used instead of 66 parts, and α, ω-diaminoPEG (Mn3) was used instead of 31 parts of (aE-5) and 3 parts of (aE-6). , 000) (aE-7) and 29 parts α, ω-diamino PTMG (Mn3,000) (anE-1) were used [the HLB of the two mixed polyethers (a-6) was 16 ] In the same manner as in Example 5, an antistatic agent (X-6) comprising the block polymer (A-6) was obtained. The volume resistivity of (A-6) was 5 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-6) measured by DSC was 25%.

Example 7
In a stainless steel autoclave, 97 parts of (b1-1) and 5 parts of ethanolamine were charged, melted at 180 ° C. in a nitrogen gas atmosphere, and reacted at 180 ° C. for 2 hours. Thereafter, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (b1-3) having a hydroxyl group. The hydroxyl value of (b1-3) was 26.7, the amine value was 0.01, and Mn was 3,700.
Next, it was obtained by reacting 20 parts of terminal isocyanate-modified PEG (NCO content 3.0%) (aE-8) obtained by reacting PEG 3,000 and MDI, PPG (Mn 4,000) and MDI. Terminal isocyanate-modified PPG (NCO content 3.0%) (anE-2) 5 parts and bisphenol A EO adduct (Mn400) and MDI and EO adduct (NCO content) 3.0%) (aE-9) 3 parts [The HLB of the three kinds of mixed polyethers (a-7) is 16], and 48 parts of the modified polypropylene (b1-3) having a hydroxyl group in a twin screw extruder The mixture is kneaded at 200 ° C. for a residence time of 30 seconds, taken out into a strand, and pelletized to form an antistatic material comprising a block polymer (A-7). It was obtained (X-7). The volume resistivity value of (A-7) was 5 × 10 ⁹ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-7) measured by DSC was 18%.

Example 8
Low molecular weight polypropylene (Mn 19,000, density 0.89, average number of double bonds per 1,000 C, 1,000 double bonds per molecule) obtained by a stainless steel autoclave 1.7 parts, content of polyolefin which can be modified at both ends (90%) 250 parts and maleic anhydride 10 parts were melted at 220 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 220 ° C. for 29 hours. I let you.
Then, excess maleic anhydride was distilled off under reduced pressure at 220 ° C. for 3 hours to obtain acid-modified polypropylene (b1-4). (B1-4) had an acid value of 5.5 and Mn19,200.
Next, 135 parts of acid-modified polypropylene (b1-4) and 10 parts of bis (2-aminoethyl) ether were melted at 200 ° C. under stirring in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polypropylene (b1-5) having amino groups at both ends. The amine value of (b1-5) was 5.8, and Mn was 19,400.
Next, in a stainless steel autoclave, 59 parts of (b1-5), 40 parts of polyethylene glycol (Mn20,000) and EO adduct of bisphenol A (aE-10) (Mn600) 1 part [the two kinds of mixed poly The HLB of ether (a-8) is 19], 5.2 parts of dodecanedioic acid, 0.3 part of antioxidant and 0.5 part of zinc acetate are charged, and 230 ° C. and a reduced pressure of 0.13 kPa or less for 15 hours. Polymerization was performed to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X-8) comprising a block polymer (A-8). The volume specific resistance value of (A-8) was 2 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (A-8) measured by DSC was 30%.

Comparative Example 1
In Example 3, the same 40 parts were used instead of 96 parts of polyamide (m-2), and replaced with 132 parts of EO product of bisphenol A (Mn3,000) (aE-1) and 15 parts of (aE-4). The antistatic agent (ratio X-1) comprising a polyetheresteramide (ratio A-1) in the same manner as in Example 3 except that 60 parts of (aE-1) [HLB 19 of the polyether] was used. Got. The volume resistivity value of (Ratio A-1) was 1 × 10 ⁹ Ω · cm, and the crystallinity of the oxyethylene group portion in (Ratio A-1) measured by DSC was 40%.

Comparative Example 2
In Example 5, 40 parts were used instead of 66 parts of (b1-2), and 31 parts of PEG (Mn6,000) (aE-5) and 3 parts of (aE-6) (aE-5) An antistatic agent (ratio X-2) comprising a block polymer (ratio A-2) was obtained in the same manner as in Example 5 except that 60 parts [HLB 20 of the polyether] was used. The volume resistivity value of (Ratio A-2) was 5 × 10 ⁸ Ω · cm, and the crystallinity of the oxyethylene group portion in (Ratio A-2) measured by DSC was 45%.

  As shown in the comparison between Example 3 and Comparative Example 1 and Example 5 and Comparative Example 2, the antistatic agent of the present invention has the same content as the content of polyoxyethylene chain. Even in the case where there is a small amount, a volume resistivity value equal to or higher than that of the comparative example using a single kind of polyether is obtained, and it can be seen that the antistatic property is excellent.

Examples 9-18, Comparative Examples 4-8
According to the formulation (parts) shown in Table 1, antistatic agents (X-1) to (X-8), (ratio X-1) to (ratio X-2), thermoplastic resin (B-1), ( B-2) and (D-1) were blended and blended for 3 minutes with a Henschel mixer, and then 230 ° C [when (B-1) was used] or 220 ° C [(B -2) During use] The mixture was melt-kneaded under the conditions of 100 rpm and a residence time of 5 minutes to obtain resin compositions (Examples 9 to 18) and (Comparative Examples 4 to 8).

<Performance test>
Using the resin composition obtained above, a cylinder temperature of 220 ° C. [when (B-1) is used] or 200 ° C. [(B-2) by an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] ) During use], a test piece was prepared by molding at a mold temperature of 50 ° C., and performance evaluation of the following items was performed. The results are shown in Table 2.

[Mechanical properties]
(1) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.
[Antistatic property]
(1) Volume resistivity value A test piece (100 × 100 mm) was measured with a superinsulator in an atmosphere of 23 ° C. and a humidity of 50% RH [according to ASTM D257].
(2) Volume resistivity value after washing with water The surface of a test piece (100 × 100 × 2 mm) leaning diagonally was washed with 100 ml of ion exchange water (23 ° C.) at a flow rate of 100 ml / min, and then circulating at 80 ° C. Dry in a dryer for 3 hours. The test piece obtained by repeating the washing-drying operation 10 times was measured in the same manner as in (1).
[Formability]
Molding was performed under the same conditions as molding with a single thermoplastic resin, and the surface condition of the molded product was visually compared with the molded product with a single thermoplastic resin according to the following evaluation criteria.
Evaluation criteria ○: Equivalent to the molded product of the thermoplastic resin alone and no irregularity ×: Concavity and convexity compared to the molded product of the thermoplastic resin alone

[Crystallinity]
The measurement method, measurement equipment, and measurement conditions are as described above.

（注）
（Ｂ−１）：ポリスチレン樹脂［商品名「ＨＩＰＳ−Ｈ０１０３」、ＰＳジャパン（株）
製］
（Ｂ−２）：ポリプロピレン樹脂［商品名「サンアロマーＰＭ７７１Ｍ」、サンアロマー
（株）製］
（Ｄ−１）：ドデシルベンゼンスルホン酸ナトリウム

(note)
(B-1): Polystyrene resin [trade name “HIPS-H0103”, PS Japan Co., Ltd.
Made]
(B-2): Polypropylene resin [Brand name "Sun Allomer PM771M", Sun Allomer
Manufactured by]
(D-1): Sodium dodecylbenzenesulfonate

  As is clear from Table 1, the molded products of the present invention (Examples 9 to 18) are superior in mechanical properties and permanent antistatic properties to the comparative molded products (Comparative Examples 4 to 8). It can be seen that even when washed with water, the volume resistivity value hardly changes, and the effect is maintained semipermanently.

  Since the molded product formed by molding the antistatic resin composition of the present invention is excellent in antistatic properties and mechanical properties, housing products for home appliances (TVs, etc.), OA equipment, game equipment, office equipment, etc., IC Widely used in various plastic containers such as trays, tape substrates for semiconductor manufacturing processes, films for various packaging materials, sheets for flooring, artificial turf, mats, automobile parts, etc. that require permanent antistatic properties. Can be extremely useful.

Claims (6)

Mixture of two or more polyethers having an oxyethylene group (aE), or a mixture of at least one polyether having an oxyethylene group (aE) and a polyether having no oxyethylene group (anE) Of the copolymer (A) containing the block of the polyether (a) of HLB 16 to 20 as a constituent unit, and comprising the oxyethylene group part of (A) measured by the differential scanning calorimetry (DSC) method An antistatic agent (X) having a crystallinity of 0 to 30% , wherein the (A) is at least one selected from the group consisting of the following (A1) and (A2 ).
(A1): A polyether ester amide derived from a polyamide and a polyether composed of an alkylene oxide adduct (number average molecular weight 300 to 5,000) of a bisphenol compound and / or a polyalkylene glycol.
(A2): A structure in which a polyolefin block and a polyether block are repeatedly and alternately bonded through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. A block polymer. The proportion of the polyether (aE) having an oxyethylene group is 80 to 100% based on the weight of the polyether (a). Antistatic agent (X) of description. An antistatic resin composition comprising the thermoplastic resin (B) containing the antistatic agent (X) according to claim 1 or 2 . The composition according to claim 3 , wherein the weight ratio of (X) to (B) is from 1/99 to 40/60. An antistatic resin molded article obtained by molding the composition according to claim 3 or 4 . A molded article obtained by coating and / or printing the molded article according to claim 5 .