Antistatic agent

Abstract

The object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to thermoplastic resins. [Solution] An antistatic agent (Z) comprising a block polymer (A) having blocks of hydrophobic polymer (a) and blocks of hydrophilic polymer (b) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and at least one salt (S2) selected from the group consisting of alkali metal halides and alkali metal halides.

Description

[Technical Field]

[0001] This invention relates to an antistatic agent. [Background technology]

[0002] Conventionally, it is common to use antistatic agents to impart antistatic properties to thermoplastic resins with high insulating properties. One known method for imparting antistatic properties using antistatic agents is to knead a small amount of polyether ester amide (see, for example, Patent Document 1), which is a polymer-type antistatic agent, into the resin. However, even with the method of incorporating the polymer-type antistatic agent described above, the antistatic properties were not entirely satisfactory. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 08-12755 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to thermoplastic resins. [Means for solving the problem]

[0005] The present inventors have arrived at the present invention as a result of their research to achieve the above objective. That is, the present invention is an antistatic agent (Z) comprising a block polymer (A) having a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and at least one salt (S2) selected from the group consisting of alkali metal halides and alkaline earth metal halides. [Effects of the Invention]

[0006] The antistatic agent (Z) of the present invention has the following effects. (1) It imparts excellent antistatic properties. (2) It imparts excellent antistatic properties at low temperatures to thermoplastic resins. (3) It is excellent in non - contamination of the cooling roll during molding.

Mode for Carrying Out the Invention

[0007] <Hydrophobic polymer (a)> Examples of the hydrophobic polymer (a) in the present invention include polyamide (a1) and polyolefin (a2). Among the above - mentioned hydrophobic polymers (a), from the viewpoint of antistatic properties, polyamide (a1) and polyolefin (a2) are preferable, and polyolefin (a2) is more preferable. The hydrophobic polymer (a) in the present invention preferably has a volume resistivity exceeding 1×10 11 Ω·cm. The volume resistivity in the present invention is a value obtained by measuring in an atmosphere of 23°C and 50% RH in accordance with ASTM D257 (1984). The above (a) may be used alone or in combination of two or more.

[0008] <Polyamide (a1)> The polyamide (a1) in the present invention includes those obtained by ring - opening polymerization or polycondensation of amide - forming monomers (a10). Examples of the amide - forming monomer (a10) include lactam (a101) and aminocarboxylic acid (a102). A combination of diamine (a103) and dicarboxylic acid (a104) may also be used as the amide - forming monomer (a10). Specifically, examples of the polyamide (a1) include those obtained by ring - opening polymerization or polycondensation of lactam (a101) and aminocarboxylic acid (a102), and polycondensates of diamine (a103) and dicarboxylic acid (a104), etc.

[0009] Examples of lactams (a101) include lactams with 4 to 20 carbon atoms (hereinafter sometimes abbreviated as C) such as γ-lactam, δ-lactam, ε-caprolactam, enantractam, capryllactam, ω-laurolactam, and undecanolactam. Examples of ring-opening polymers of lactam (a101) include nylon 4, nylon 5, nylon 6, nylon 7, nylon 8, nylon 11, and nylon 12.

[0010] Examples of aminocarboxylic acids (a102) include C6-C12 aminocarboxylic acids (e.g., ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and mixtures thereof).

[0011] Examples of diamines (a103) include C2-40 diamines, such as aliphatic, alicyclic, and aromatic (aliphatic) diamines, and mixtures thereof. Examples of aliphatic diamines include C2-40 aliphatic diamines (e.g., ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and 1,20-eicosanediamine). Examples of alicyclic diamines include C5-40 alicyclic diamines (e.g., 1,3- or 1,4-cyclohexanediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane, and 2,2-bis(4-aminocyclohexyl)propane). Examples of aromatic diamines include C6-40 aromatic diamines (e.g., p-phenylenediamine, 2,4- or 2,6-toluylenediamine, and 2,2-bis(4,4'-diaminophenyl)propane). Examples of aromatic aliphatic diamines include C7-20 aromatic aliphatic diamines (e.g., xylylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene, and bis(aminobutyl)benzene).

[0012] Examples of dicarboxylic acids (a104) include C2-40 dicarboxylic acids, such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids [e.g., acid anhydrides, lower (C1-4) alkyl esters and dicarboxylic acid salts [e.g., alkali metal salts (e.g., lithium salts, sodium salts and potassium salts)]] and mixtures of two or more of these.

[0013] Examples of aliphatic dicarboxylic acids include C2-40 (preferably C4-20, and more preferably C6-12, from the viewpoint of antistatic properties) aliphatic dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, maleic acid, fumaric acid, and itaconic acid). Examples of aromatic ring-containing dicarboxylic acids include C8-40 (preferably C8-16, and more preferably C8-14, from the viewpoint of antistatic properties) aromatic ring-containing dicarboxylic acids (e.g., orthophthalic acid, isophthalic acid, terephthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylenedicarboxylic acid, xylylenedicarboxylic acid, and alkali metal (same as above) salts of 5-sulfoizophthalate). Examples of alicyclic dicarboxylic acids include C5-40 (preferably C6-18, and more preferably C8-14, from the viewpoint of antistatic properties) alicyclic dicarboxylic acids (e.g., cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and camphor acid, etc.).

[0014] Of the above amide-forming monomers (a10), ε-caprolactam and 12-aminododecanoic acid are preferred from the viewpoint of antistatic properties, and it is also preferable to combine adipic acid and hexamethylenediamine to form the amide-forming monomer (a10).

[0015] Methods for producing polyamide (a1) include ring-opening polymerization or polycondensation of the amide-forming monomer (a10) in the presence of a molecular weight modifier. Either a diamine or a dicarboxylic acid can be used as the molecular weight modifier. As the diamine and dicarboxylic acid, one or more of the compounds described above can be used as the diamine (a103) (C2-40, preferably C4-20) and the dicarboxylic acid (a104) (C2-40, preferably C4-20), respectively.

[0016] The amount of the molecular weight modifier used is preferably 2 to 80% by weight, and more preferably 4 to 75% by weight, based on the total weight of the amide-forming monomer (a10) and the molecular weight modifier, from the viewpoint of antistatic properties.

[0017] The number-average molecular weight of polyamide (a1) [hereinafter abbreviated as Mn; measured by gel permeation chromatography (GPC)] is preferably 200 to 10,000, more preferably 500 to 6,000, and particularly preferably 1,000 to 5,000, from the viewpoint of antistatic properties and moldability.

[0018] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymer in this invention can be measured using gel permeation chromatography (GPC) under the following conditions. • Device (example): "HLC-8120" [Manufactured by Tosoh Corporation] • Column (example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 pieces) "TSKgelMultiporeHXL-M" [Manufactured by Tosoh Corporation] (1 bottle) • Sample solution: 0.3% by weight orthodichlorobenzene solution ·Solution injection volume: 100μl ·Flow rate: 1ml / min ·Measurement temperature: 135℃ • Detection device: Refractive index detector • Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE) 12 samples (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [Manufactured by Tosoh Corporation]

[0019] <Polyolefin (a2)> In the present invention, polyolefin (a2) is preferably a polyolefin having a reactive group. Examples of polyolefin (a2) include polyolefin (a21) having reactive groups at both ends and polyolefin (a22) having a reactive group at one end. Reactive groups refer to carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, amino groups, and isocyanate groups.

[0020] <Polyolefin (a21) having reactive groups at both ends> Examples of (a21) include polyolefins having carboxyl groups or carboxylic acid anhydride groups at both ends of the polymer (a21-1), polyolefins having hydroxyl groups at both ends of the polymer (a21-2), polyolefins having amino groups at both ends of the polymer (a21-3), and polyolefins having isocyanate groups at both ends of the polymer (a21-4). Of these, (a21-1) is preferred from the viewpoint of ease of modification and heat resistance during molding. In this invention, "end" refers to the terminal portion where the repeating structure of the monomer units constituting the polymer is interrupted. Furthermore, "both ends" refers to both ends of the polymer's main chain.

[0021] (a21) can be obtained, for example, by introducing a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, or an isocyanate group to both ends of a polyolefin (a21-0) whose main component is a polyolefin whose ends are modifiable. Furthermore, "main component" means that the weight of polyolefins with modifiable ends, relative to the total weight of the polyolefin, is 50% by weight or more of the total weight of the polyolefin. However, even if the weight of polyolefins with modifiable ends is less than 50% by weight of the total weight of polyolefins, if the sum of the weight of polyolefins with modifiable ends and the weight of polyolefins with modifiable ends (described later) is 50% by weight or more of the total weight of polyolefins, and the weight of polyolefins with modifiable ends is equal to or greater than the weight of polyolefins with modifiable ends, then (a21-0) shall apply.

[0022] (a21-0) includes polyolefins obtained by (co)polymerization of one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms), containing 30 mol% or more of propylene-derived structural units in the polyolefin, and reduced polyolefins {those obtained by mechanically, thermally, or chemically reducing high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 10,000 to 150,000] polyolefins}. Note that (co)polymerization means polymerization or copolymerization.

[0023] Of these, deconstituted polyolefins are preferred from the viewpoint of ease of modification when introducing carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, amino groups, or isocyanate groups, and ease of availability, and thermally deconstituted polyolefins are even more preferred. By thermal deconstitution, as described later, low molecular weight polyolefins with 1 to 2 terminal double bonds per molecule can be easily obtained, and these low molecular weight polyolefins can be easily modified by introducing carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, amino groups, or isocyanate groups.

[0024] Examples of thermally deconjugated polyolefins include those obtained by heating high molecular weight polyolefins in an inert gas (at 300-450°C for 0.5-10 hours, for example, by the method described in Japanese Patent Publication No. 3-62804) and those that have been thermally deconjugated by heating in air.

[0025] Examples of high molecular weight polyolefins used in the thermal reduction method include (co)polymers of one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10) [Mn is preferably 10,000 to 150,000, more preferably 15,000 to 70,000; melt flow rate (hereinafter abbreviated as MFR: unit is g / 10min) is preferably 0.5 to 150, more preferably 1 to 100], which have 30 mol% or more of propylene-derived constituent units in the polyolefin. Here, MFR is a numerical value representing the melt viscosity of the resin, and a larger value indicates a lower melt viscosity. The measurement of MFR conforms to the method specified in JIS K7210-1 (2014). For example, in the case of polypropylene, it is measured under conditions of 230°C and a load of 2.16 kgf. Examples of olefins having 2 to 30 carbon atoms include α-olefins with 2 to 30 carbon atoms and dienes with 4 to 30 carbon atoms.

[0026] Examples of α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene, and 1-tetracosene. Examples of dienes with 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene, and 1,11-dodecadiene. Among olefins having 2 to 30 carbon atoms, those preferred from the viewpoint of molecular weight control are α-olefins having 2 to 12 carbon atoms, butadiene, isoprene, and mixtures thereof; more preferred are α-olefins having 2 to 10 carbon atoms, butadiene, and mixtures thereof; and particularly preferred are ethylene and propylene, which are α-olefins having 2 to 3 carbon atoms, and mixtures thereof.

[0027] <Polyolefin (a22) having a reactive group at one end> Examples of (a22) include polyolefins having a carboxyl group or a carboxylic acid anhydride group at one end of the polymer (a22-1), polyolefins having a hydroxyl group at one end of the polymer (a22-2), polyolefins having an amino group at one end of the polymer (a22-3), polyolefins having an isocyanate group at one end of the polymer (a22-4), and polyolefins having both a carboxyl group and a hydroxyl group at one end of the polymer (a22-5). Of these, (a22-1) is preferred from the viewpoint of ease of modification and heat resistance during molding. Note that "one end" refers to either end of the polymer's main chain.

[0028] (a22) can be obtained, for example, by introducing a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, or an isocyanate group into a polyolefin (a22-0) whose main component is a polyolefin with one end that can be modified. Furthermore, "main component" means that the weight of polyolefin with one end that can be modified accounts for 50% or more of the total weight of the polyolefin. However, even if the weight of polyolefins with one end that can be modified is less than 50% by weight of the total weight of polyolefins, if the sum of the weight of polyolefins with one end that can be modified and the weight of polyolefins with both ends that can be modified as described above is 50% by weight or more of the total weight of polyolefins, and the weight of polyolefins with one end that can be modified is greater than the weight of polyolefins with both ends that can be modified, then (a22-0) shall apply.

[0029] (a22-0) can be obtained in the same way as (a21-0).

[0030] (a21-0) and (a22-0) are generally obtained as a mixture thereof, but the mixture may be used as is or after purification and separation. Of these, the mixture is preferred from the viewpoint of manufacturing cost, etc.

[0031] The following describes (a21-1) to (a21-4), which have a carboxyl group, carboxylic acid anhydride group, hydroxyl group, amino group, or isocyanate group at both ends of (a21-0). However, (a22-1) to (a22-4), which have one of these groups at one end of (a22-0), can be obtained in the same manner as (a21-1) to (a21-4) by replacing (a21-0) with (a22-0). The same applies to preferred forms (a21) and (a22).

[0032] As (a21-1), polyolefins having a structure in which the terminal end of (a21-0) is modified with an α,β-unsaturated carboxylic acid (anhydride) (a21-1-1), polyolefins having a structure in which (a21-1-1) is secondarily modified with a lactam or aminocarboxylic acid (a21-1-2), polyolefins having a structure in which (a21-0) is modified by oxidation or hydroformylation (a21-1-3), polyolefins having a structure in which (a21-1-3) is secondarily modified with a lactam or aminocarboxylic acid (a21-1-4), and mixtures of two or more of these can be used. Note that α,β-unsaturated carboxylic acid (anhydride) refers to an α,β-unsaturated carboxylic acid or its anhydride.

[0033] (a21-1-1) can be obtained by modifying (a21-0) with an α,β-unsaturated carboxylic acid (anhydride). Examples of α,β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids, and anhydrides of mono or dicarboxylic acids, specifically (meth)acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), and citraconic acid (anhydride). Of these, from the viewpoint of ease of modification, mono- or dicarboxylic acid anhydrides and dicarboxylic acids are preferred, more preferably maleic acid (anhydride) and fumaric acid, and particularly preferred maleic acid (anhydride). Note that (meth)acrylic acid means acrylic acid or methacrylic acid.

[0034] (a21-1-2) can be obtained by secondarily modifying (a21-1-1) with the lactam or aminocarboxylic acid.

[0035] (a21-1-3) can be obtained by oxidizing (a21-0) with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation using the oxo method. The introduction of carboxyl groups by oxidation can be carried out by known methods, such as the method described in U.S. Patent No. 3,692,877. The introduction of carboxyl groups by hydroformylation can be carried out by various methods, including known methods, such as the method described in Macromolecules, Vol. 31, p. 5943. (a21-1-4) can be obtained by secondarily modifying (a21-1-3) with a lactam or aminocarboxylic acid.

[0036] The acid value of (a21-1) is preferably 4 to 100 mg KOH / g, more preferably 4 to 50 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b). The acid value in this invention can be measured in accordance with JIS K 0070.

[0037] For (a21-2), (a21-1) can be modified with an amine having a hydroxyl group, resulting in a polyolefin having a hydroxyl group, or a mixture of two or more of these. Examples of hydroxyl group-containing amines that can be used for denaturation include amines having hydroxyl groups with 2 to 10 carbon atoms, specifically 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, and 3-aminomethyl-3,5,5-trimethylcyclohexanol.

[0038] The hydroxyl value of (a21-2) is preferably 4 to 100 mg KOH / g, more preferably 4 to 50 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b). The hydroxyl value in this invention can be measured in accordance with JIS K 0070.

[0039] For (a21-3), (a21-1) can be a polyolefin having an amino group modified with a diamine, or a mixture of two or more of these. Diamines with 2 to 12 carbon atoms can be used, specifically including ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and decamethylenediamine. Of these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine, etc.) are preferred from the viewpoint of ease of modification, ethylenediamine and hexamethylenediamine are more preferred, and ethylenediamine is particularly preferred.

[0040] The amine value of (a21-3) is preferably 4 to 100 mg KOH / g, more preferably 4 to 50 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b). The amine value in this invention can be measured in accordance with JIS K 1557-7.

[0041] Examples of (a21-4) include polyolefins having isocyanate groups obtained by modifying (a21-2) with poly(2-3 or more) isocyanates, and mixtures of two or more of these. Polyisocyanates include aromatic polyisocyanates with 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate group; the same applies hereinafter), aliphatic polyisocyanates with 2 to 18 carbon atoms, alicyclic polyisocyanates with 4 to 15 carbon atoms, aromatic aliphatic polyisocyanates with 8 to 15 carbon atoms, modified forms of these polyisocyanates, and mixtures of two or more of these.

[0042] For (a22-5), a polyolefin (a22-5-1) can be used, which has a structure in which one end of (a22-0) is modified with an α,β-unsaturated carboxylic acid anhydride, and then further modified with a diolamine. Examples of diolamines used for secondary modification include diethanolamine.

[0043] The Mn values ​​of (a21) and (a22) are preferably 1,000 to 25,000, more preferably 1,500 to 12,000, and particularly preferably 2,000 to 7,000, respectively, from the viewpoint of antistatic properties.

[0044] <Hydrophilic polymer (b)> Examples of the hydrophilic polymer (b) in the present invention include the hydrophilic polymer described in Japanese Patent No. 3488163, specifically polyether (b1), polyether-containing hydrophilic polymer (b2), etc. Polyether (b1) is preferred from the viewpoint of antistatic properties and resin properties. In this invention, the hydrophilic polymer (b) is preferably 1 × 10 11 The polymer has a volume resistivity of Ω·cm or less. Furthermore, (b) above may be used alone or in combination of two or more types.

[0045] Examples of polyethers (b1) include polyetherdiols (b1-1), polyetherdiamines (b1-2), and modified products thereof (b1-3). Examples of polyetherdiols (b1-1) include those obtained by the addition reaction of an alkylene oxide (hereinafter abbreviated as AO) to a diol (b0), and specifically those represented by general formula (1).

[0046] H-(OR 1 ) a -OE 1 -O-(R 2 O) b -H (1) E in general formula (1) 1 is the residue obtained by removing all hydroxyl groups from diol (b0). R in general formula (1) 1 and R 2 are each independently an alkylene group having 2 to 4 carbon atoms, an alkylene group having 5 to 12 carbon atoms, a styrene group, and a chloromethyl group. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, 1,2- or 1,3-propylene group, and 1,2-, 1,3-, 1,4- or 2,3-butylene group, etc. a and b in general formula (1) are the average addition molar numbers of (OR 1 ) and (R 2 O), and are each independently 1 to 300, preferably 2 to 250, more preferably 10 to 100. When a and b in general formula (1) are each 2 or more, R 1 , R 2 may be the same or different, and the (OR 1 ) a , (R 2 O) b moieties may be randomly bonded or block-bonded.

[0047] Examples of the diol (b0) include aliphatic dihydric alcohols having 2 to 12 carbon atoms, alicyclic dihydric alcohols having 5 to 12 carbon atoms, aromatic dihydric alcohols having 6 to 18 carbon atoms, and tertiary amino group-containing diols, etc.

[0048] Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di(hydroxymethyl)cyclohexane and 1,5-di(hydroxymethyl)cycloheptane, etc. Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (such as xylylenediol, hydroquinone, catechol, resorcinol, and urushiol) and polycyclic aromatic dihydric alcohols (such as bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxynaphthalene, and binaphthol).

[0049] Examples of tertiary amino group-containing diols include bishydroxyalkylated compounds of aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (such as methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, and dodecylamine) and bishydroxyalkylated compounds of aromatic primary amines having 6 to 12 carbon atoms (such as aniline and benzylamine). Of these, preferred diols (b0) from the viewpoint of reactivity with bishydroxyalkylated compounds are aliphatic dihydric alcohols having 2 to 12 carbon atoms and aromatic dihydric alcohols having 6 to 18 carbon atoms, and more preferably EG and bisphenol A.

[0050] Polyetherdiol (b1-1) can be produced by adding AO to diol (b0). As for AOs, carbon-2 to carbon-4 AOs [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, and combinations of two or more of these are used, but if necessary, other AOs [α-olefin oxides with 5 to 12 carbon atoms, styrene oxide, and epihalohydrins (epichlorohydrin, etc.)] can also be used in small proportions (30% by weight or less based on the total weight of AOs). When using two or more AOs together, the combination can be random or block. Preferred AOs are EOs alone and EOs combined with other AOs.

[0051] The addition reaction of AO can be carried out by known methods, for example, in the presence of an alkaline catalyst, at a temperature of 100-200°C. Based on the weight of polyetherdiol (b1-1) represented by general formula (1), (OR 1 ) a and (R 2 O) b The content is preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight. (OR 1 ) a and (R 2 O) b The oxyethylene group content based on weight is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly preferably 50 to 100% by weight, and most preferably 60 to 100% by weight. As the polyetherdiol (b1-1), EO adducts of bisphenol A and polyethylene glycol are preferred.

[0052] Examples of polyetherdiamines (b1-2) include those represented by general formula (2). H2N-R 3 -(OR 4 ) c -OE 2 -O-(R 5 O)4R 6 -NH2(2)

[0053] E in general formula (2) 2 This is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of diol (b0) are the same as those exemplified for polyetherdiol (b1-1) above, and the preferred range is also the same. R in general formula (2) 3 , R 4 , R 5 and R 6These are, independently, an alkylene group having 2 to 4 carbon atoms, an alkylene group having 5 to 12 carbon atoms, a styrene group, and a chloromethyl group. The alkylene group having 2 to 4 carbon atoms is R in general formula (1). 1 and R 2 Examples similar to those given as illustrations can be cited. In general formula (2), c and d are (OR 4 ) and (R 5 This is the average number of moles added to O), and each is independently between 1 and 300, preferably between 2 and 250, and more preferably between 10 and 100. R when c and d in general formula (2) are both 2 or greater 4 , R 5 They may be the same or different, (OR 4 ) c , (R 5 O) d The parts can be either random joins or block joins.

[0054] Polyetherdiamine (b1-2) can be obtained by converting all the hydroxyl groups of polyetherdiol (b1-1) to alkylamino groups. For example, it can be produced by reacting polyetherdiol (b1-1) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

[0055] Examples of modified products (b1-3) include aminocarboxylic acid modified products (terminal amino group), isocyanate modified products (terminal isocyanate group), and epoxy modified products (terminal epoxy group) of polyetherdiol (b1-1) or polyetherdiamine (b1-2). Aminocarboxylic acid modified products can be obtained by reacting a polyetherdiol (b1-1) or polyetherdiamine (b1-2) with an aminocarboxylic acid or lactam. Isocyanate-modified products can be obtained by reacting a polyetherdiol (b1-1) or polyetherdiamine (b1-2) with a polyisocyanate, or by reacting a polyetherdiamine (b1-2) with phosgene. Epoxy-modified products can be obtained by reacting a polyetherdiol (b1-1) or polyetherdiamine (b1-2) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, and alicyclic diepoxide: epoxy equivalent 85-600), or by reacting a polyetherdiol (b1-1) with an epihalohydrin (such as epichlorohydrin).

[0056] The Mn content of the hydrophilic polymer (b) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15,000, and most preferably 1,200 to 8,000, from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (a).

[0057] <Block polymer (A)> The block polymer (A) in the antistatic agent (Z) of the present invention has a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b) as constituent units. The hydrophobic polymer (a) and hydrophilic polymer (b) constituting the block polymer (A) may each be one or two or more types.

[0058] The weight ratio [hydrophobic polymer (a) / hydrophilic polymer (b)] of the blocks of hydrophobic polymer (a) and hydrophilic polymer (b) constituting the block polymer (A) is preferably 10 / 90 to 80 / 20, and more preferably 20 / 80 to 75 / 25, from the viewpoint of antistatic properties and water resistance.

[0059] The structures formed by the bonding of a block polymer (A) consisting of a hydrophobic polymer (a) and a block polymer (b) include the (a)-(b) type, (a)-(b)-(a) type, (b)-(a)-(b) type, and the [(a)-(b)]n type (where n represents the average number of repeats). From the viewpoint of conductivity, the structure of the block polymer (A) is preferably of the [(a)-(b)]n type, in which hydrophobic polymers (a) and hydrophilic polymers (b) are repeatedly and alternately bonded. In the [(a)-(b)]n-type structure, n is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10, from the viewpoint of antistatic properties and mechanical strength (mechanical properties). n is the Mn of the block polymer (A) and 1 This can be determined by 1H-NMR analysis.

[0060] The Mn content of block polymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 60,000, and particularly preferably 10,000 to 40,000, from the viewpoint of the mechanical strength (mechanical properties) and antistatic properties of the molded article described later.

[0061] If the block polymer (A) has a structure in which a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b) are linked via ester bonds, amide bonds, ether bonds, or imide bonds, it can be produced by the following method. Of the above bonds, ester bonds and amide bonds are preferred from an industrial standpoint.

[0062] One method involves placing a hydrophobic polymer (a) and a hydrophilic polymer (b) into a reaction vessel and reacting them for 1 to 50 hours under stirring at a reaction temperature of 100 to 250°C and a pressure of 0.003 to 0.1 MPa, while removing the water produced by the amidation, esterification, or imidation reaction (hereinafter abbreviated as "produced water") from the reaction system. The weight ratio of the hydrophobic polymer (a) to the hydrophilic polymer (b) used in the reaction [hydrophobic polymer (a) / hydrophilic polymer (b)] is 10 / 90 to 80 / 20, and more preferably 20 / 80 to 75 / 25, from the viewpoint of antistatic properties and water resistance.

[0063] In the case of esterification reactions, it is preferable to use 0.05 to 0.5% by weight of a catalyst based on the total weight of the hydrophobic polymer (a) and the hydrophilic polymer (b) to promote the reaction. Examples of catalysts include inorganic acids (sulfuric acid and hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid, etc.), antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide and dibutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, bistriethanolamine titanate, and potassium titanate oxalate, etc.), zirconium catalysts (tetrabutylzirconate, zirconium oxyacetate, etc.), and zinc catalysts (zinc acetate, etc.). If a catalyst is used, it can be neutralized as necessary after the esterification reaction is complete, and the catalyst can be removed and purified by treatment with an adsorbent.

[0064] The following methods can be used to remove the generated water from the reaction system. (1) A method of removing only the generated water from the reaction system by azeotroping the organic solvent and the generated water under reflux using an organic solvent that is immiscible with water (e.g., toluene, xylene, and cyclohexane). (2) A method of blowing a carrier gas (e.g., air, nitrogen, helium, argon, and carbon dioxide) into the reaction system and removing the generated water from the reaction system along with the carrier gas. (3) A method of removing the generated water from the reaction system by reducing the pressure inside the reaction system.

[0065] <Alkyl (alkyl group with 6-18 carbon atoms) benzenesulfonate (S1)> In the present invention, an example of an alkyl (alkyl group with 6 to 18 carbon atoms) benzenesulfonate (S1) is dodecylbenzenesulfonate. The number of carbon atoms in the alkyl group of (S1) is preferably 8 to 16, and more preferably 10 to 14.

[0066] Examples of cations that constitute sulfonates (S1) include alkali metal cations (e.g., lithium, sodium, potassium) and imidazolium cations.

[0067] The above imidazolium cations include C5-15 imidazolium cations, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, and 1,3-dimethylimidazolium. Methyl-2-ethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyano- Examples include anomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolium, 3-methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, and 2-hydroxyethyl-1,3-dimethylimidazolium.

[0068] Among the cations constituting the salt (S1), from the viewpoint of antistatic properties, sodium and imidazolium are preferred, more preferably sodium and 1-alkyl(alkyl with 1 to 3 carbon atoms)3-alkyl(alkyl with 1 to 3 carbon atoms)imidazolium, and particularly preferred is 1-ethyl-3-methylimidazolium.

[0069] <Salt (S2)> In this invention, salt (S2) is at least one salt selected from the group consisting of alkali metal halides and alkaline earth metal halides. Salt (S2) is any salt other than (S1) described above.

[0070] Examples of cations that make up salts (S2) include alkali metal cations (e.g., lithium, sodium, potassium) and alkaline earth metal cations (e.g., magnesium, calcium). Among the cations constituting the above salt (S2), alkali metal ions are preferred.

[0071] Examples of anions that make up a salt (S2) include halide ions (chloride ions, bromide ions). Among the anions that make up the above salt (S2), chloride ions and bromide ions are preferred.

[0072] Of the above salts (S2), alkali metal halides (e.g., lithium chloride, sodium chloride) are preferred.

[0073] <Antistatic agent (Z)> The antistatic agent (Z) of the present invention comprises the block polymer (A), the salt (S1), and the salt (S2). This antistatic agent (Z), due to its composition of (A), (S1), and (S2), is presumed to have excellent antistatic and non-contaminating properties because it is appropriately mixed / dispersed in the thermoplastic resin (E).

[0074] The weight ratio [(A) / {(S1)+(S2)}] of the block polymer (A) to the total weight of the sulfonate (S1) and salt (S2) is preferably 75 / 25 to 98 / 2, and more preferably 85 / 15 to 96 / 4. The weight ratio of salt (S1) to salt (S2) [(S1) / (S2)] is preferably 6 / 94 to 70 / 30, and more preferably 25 / 75 to 60 / 40.

[0075] The antistatic agent (Z) can be manufactured, for example, by one of the following methods (1) or (2). (1) Mix the block polymer (A), salt (S1), and salt (S2). (2) When a polymer from hydrophobic block (a) and a polymer from hydrophilic block (b) are reacted by a known method to obtain block polymer (A), salt (S1) and salt (S2) are added before or during the reaction.

[0076] <Antistatic resin composition (Y)> The antistatic resin composition (Y) of the present invention contains the above-mentioned antistatic agent (Z) and the thermoplastic resin (E) described later. The weight ratio of the antistatic agent (Z) to the thermoplastic resin (E) [antistatic agent (Z) / thermoplastic resin (E)] is preferably 3 / 97 to 20 / 80, and more preferably 5 / 95 to 15 / 85, from the viewpoint of antistatic properties and mechanical strength (mechanical properties).

[0077] Thermoplastic resins (E) include polyphenylene ether resin (E1); vinyl resins [polyolefin resins (E2) [e.g., polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], poly(meth)acrylic resins (E3) [e.g., polymethyl methacrylate], polystyrene resins (E4) [vinyl group-containing aromatic hydrocarbons alone, or copolymers comprising vinyl group-containing aromatic hydrocarbons and at least one selected from the group consisting of (meth)acrylic acid esters, (meth)acrylonitrile and butadiene, e.g., polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS)]. Examples include: resins (E5) [e.g., polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resins (E6) [e.g., nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6 / 66, nylon 6 / 12]; polycarbonate resins (E7) [e.g., polycarbonate (PC), polycarbonate / ABS alloy resin]; polyacetal resins (E8); and mixtures of two or more of these.

[0078] Of these, from the viewpoint of the mechanical strength (mechanical properties) and antistatic properties of the molded product described later, polyolefin resin (E2), polystyrene resin (E4), and polycarbonate resin (E7) are preferred, and polyolefin resin (E2) and polycarbonate resin (E7) are even more preferred.

[0079] The antistatic resin composition (Y) of the present invention may optionally contain known resin additives (G) in addition to the block polymer (A), salt (S1), salt (S2), and thermoplastic resin (E), as long as they do not impair the effects of the present invention. Examples of resin additives (G) include compatibilizers (such as carboxylic acid-modified polypropylene), flame retardants (such as guanamine), pigments (such as titanium dioxide), dyes (such as azo dyes), nucleating agents (such as talc), lubricants (such as carnauba wax), plasticizers (such as dioctyl phthalate), antioxidants (such as triphenyl phosphite), and ultraviolet absorbers [such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole]. The content of the resin additive (G) varies depending on the application, but based on the total weight of the antistatic agent (Z) and the thermoplastic resin (E), it is, for example, 45% by weight or less, preferably 0.01 to 30% by weight, and more preferably 0.1 to 10% by weight, from the viewpoint of additive effect.

[0080] The antistatic resin composition (Y) of the present invention is obtained by melt-mixing the above-mentioned antistatic agent (Z), thermoplastic resin (E), and optionally a resin additive (G). As for the melt-mixing method, a generally applicable method is to mix the pelletized or powdered components in a suitable mixer, such as a Henschel mixer, and then melt-mix them in an extruder to form pellets. There are no particular restrictions on the order in which each component is added during melt mixing, but for example, (1) A method of melting and mixing together an antistatic agent (Z), a thermoplastic resin (E), and, if necessary, a resin additive (G). (2) A method is to prepare a high-concentration resin composition (masterbatch resin composition) of the antistatic agent (Z) by pre-melting and mixing a portion of the antistatic agent (Z) and the thermoplastic resin (E), and then melt-mixing the remaining thermoplastic resin (E) and, if necessary, a resin additive (G).

[0081] <Molded products> The molded article of the present invention is obtained by molding the above-mentioned antistatic resin composition (Y). Examples of molding methods include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (casting method, tenter method, inflation method, etc.), and the article can be molded by any method depending on the purpose.

[0082] The antistatic agent (Z) of the present invention imparts excellent antistatic properties to thermoplastic resins (E), and is particularly excellent at low temperatures. Furthermore, it exhibits excellent non-contamination of cooling rolls during molding. Therefore, it can be widely used as a material for housing products [for home appliances, office equipment, game consoles, and office equipment, etc.] molded by various molding methods [injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (e.g., casting method, tenter method, and inflation method)], plastic container materials [trays used in clean rooms (IC trays, etc.), other containers, etc.], various cushioning materials, covering materials (packaging films, protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automobile parts, etc.), making it extremely useful. [Examples]

[0083] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, parts refer to parts by weight.

[0084] <Manufacturing Example 1> [Production of polyolefins having carboxyl groups at both ends (a-1)] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 90 parts of low molecular weight polypropylene obtained by thermal reduction [polypropylene (MFR: 10 g / 10 min) was thermally reduced at 410 ± 0.1 °C under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefins that can be modified at both ends: 90% by weight], 10 parts of maleic anhydride, and 30 parts of xylene were added and uniformly mixed. After purging with nitrogen, the mixture was sealed and heated to 200 °C while stirring to melt it, and the reaction was carried out at the same temperature for 10 hours. Next, excess maleic anhydride and xylene were removed by distillation under reduced pressure (0.013 MPa or less) at 200°C for 3 hours to obtain polyolefin (a-1) having carboxyl groups at both ends of the polymer. The acid value of (a-1) was 27.5 and the Mn was 3,600.

[0085] <Manufacturing Example 2> [Production of polyolefin (a-1-1) obtained by secondary modification of polyolefin (a-1)] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 78.3 parts of polyolefin (a-1) and 21.7 parts of ε-caprolactam were added and uniformly mixed. After mixing, the temperature was raised to 200°C under a nitrogen gas atmosphere while stirring, and the reaction was carried out at the same temperature under a sealed container for 3 hours to obtain polyolefin (a-1-1) through secondary modification of polyolefin (a-1). The acid value of polyolefin (a-1-1) was 21.5, and the Mn content was 4,700.

[0086] <Manufacturing Example 3> [Production of polyamide (a-2)] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 79.4 parts of ε-caprolactam, 11.5 parts of terephthalic acid, 0.3 parts of antioxidant ["Irganox 1010", manufactured by BASF Japan Ltd.], and 6 parts of water were added. After purging with nitrogen, the mixture was heated to 220°C under a sealed container while stirring, and stirred at the same temperature (pressure: 0.2~0.3 MPa) for 4 hours to obtain polyamide (a-2) having carboxyl groups at both ends. The acid value of (a-2) was 78, and the Mn content was 1,400.

[0087] <Manufacturing Example 4> [Production of polyamide (a-3)] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 82.5 parts of ω-laurolactam, 16.3 parts of terephthalic acid, 0.3 parts of antioxidant ["Irganox 1010", manufactured by BASF Japan Ltd.], and 10 parts of water were added. After purging with nitrogen, the mixture was heated to 220°C under a sealed container while stirring, and stirred at the same temperature (pressure: 0.2~0.3 MPa) for 4 hours to obtain polyamide (a-3) having carboxyl groups at both ends. The acid value of (a-3) was 109 and the Mn was 1,000.

[0088] <Manufacturing Example 5> [Production of modified polyolefins (a-1-2) having hydroxyl groups at both ends of the polymer] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and vacuum device, 95 parts of polyolefin (a-1) and 5 parts of 2-aminoethanol were melted at 180°C under a nitrogen gas atmosphere and reacted at 180°C for 2 hours. Subsequently, the excess 2-aminoethanol was removed by distillation under reduced pressure at 180°C for 2 hours to obtain modified polyolefin (a1-1-2) having hydroxyl groups at both ends of the polymer. The hydroxyl value of modified polyolefin (a1-1-2) was 26.0, the amine value was 0.01, and the Mn was 3,900.

[0089] <Manufacturing Example 6> [Production of polyolefin (a-1-3) obtained by secondary modification of polyolefin (a-1-2)] In a pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 67.7 parts of polyolefin (a-1-2) and 32.3 parts of polyamide (a-3) were melted at 200°C under a nitrogen gas atmosphere and reacted at 200°C for 2 hours to obtain polyolefin (a-1-3) obtained by secondary modification of polyolefin (a-1-2). The acid value of the modified polyolefin (a-1-3) was 17.6 and the Mn content was 5,900.

[0090] <Manufacturing Example 11> [Synthesis of block polymer (A-1)] In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 59.5 parts of polyolefin (a-1-1) as the hydrophobic block (a) and polyetherdiol (b-1) [PEG(Mn: 3,000, volume resistivity: 1 × 10 × 7 36.7 parts of (Ω·cm), 0.5 parts of zirconium oxyacetate, and 0.3 parts of the antioxidant ["Irganox 1010", manufactured by BASF Japan Ltd.] were added, and the mixture was heated to 220°C while stirring. Polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain block polymer (A-1). The manganese content of block polymer (A-1) was 30,000, and the weight ratio [(a) / (b)] was 60 / 40.

[0091] <Manufacturing Example 12> [Block Polymer (A-2)] In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 43.8 parts of polyamide (a-2) as the hydrophobic polymer (a), 54.8 parts of bisphenol A EO adduct (b-2) (Mn: 1,800) as the hydrophilic polymer (b), and 1.4 parts of zirconium oxyacetate were added. The mixture was heated to 240°C while stirring, and polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain block polymer (A-2). The Mn of block polymer (A-2) was 22,000, and the weight ratio [(a) / (b)] was 44 / 56.

[0092] <Manufacturing Example 13> [Block Polymer (A-3)] In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 49.3 parts of polyamide (a-3) as hydrophobic polymer (a), 49.3 parts of polyethylene glycol (b-3) (Mn: 1,000) as hydrophilic polymer (b), and 1.4 parts of zirconium oxyacetate were added. The mixture was heated to 240°C while stirring, and polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 6 hours to obtain block polymer (A-3). The Mn of block polymer (A-3) was 30,000, and the weight ratio [(a) / (b)] was 50 / 50.

[0093] <Manufacturing Example 14> [Block Polymer (A-4)] In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 68.2 parts of modified polyolefin (a-1-3) as hydrophobic polymer (a), 31.0 parts of bisphenol A EO adduct (b-4) (Mn: 2,900) as hydrophilic polymer (b), 0.3 parts of antioxidant "Irganox 1010", and 0.5 parts of zirconium oxyacetate were added. The mixture was heated to 220°C while stirring, and polymerization was carried out under reduced pressure (0.013 MPa or less) at the same temperature for 3 hours to obtain a viscous block polymer (A-4). The Mn of block polymer (A-4) was 25,000, and the weight ratio [(a) / (b)] was 69 / 31.

[0094] <Example 1> In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 90 parts of block polymer (A-1), 5 parts of sodium dodecylbenzenesulfonate (S1-1), and 5 parts of lithium chloride (S2-1) were charged. The mixture was mixed and stirred at 220°C for 1 hour, then removed in strand form on a belt, pelletized, and an antistatic agent (Z-1) was obtained.

[0095] <Examples 2-6, Comparative Examples 1-3> Each antistatic agent (Z) was obtained in the same manner as in Example 1, except that the compounding composition (parts) was as shown in Table 1. The results are shown in Table 1.

[0096] [Table 1]

[0097] <Examples 11-16, Comparative Examples 11-13> According to the formulations shown in Table 2, the antistatic agent (Z) and thermoplastic resin (E) were blended in a Henschel mixer for 3 minutes. Then, the mixture was melt-kneaded at 230°C in a vented twin-screw extruder at a rotation speed of 100 rpm and a residence time of 3 minutes to obtain each antistatic resin composition (Y). Each obtained antistatic resin composition (Y) was evaluated according to the <Evaluation Method> described below. The results are shown in Table 2.

[0098] <Evaluation Method> (1) Non-contaminating cooling rolls For each antistatic resin composition (Y), an extruder equipped with a T-type die [Laboplastmill 2D20C, manufactured by Toyo Seiki Seisakusho Co., Ltd.] was used to melt-extrude the material at a cylinder temperature of 230°C. While taking up at a take-up speed of 2 m / min, the material was rapidly cooled on a cooling roll at 20°C to form an extruded sheet with a thickness of 500 μm for 2 hours. After that, the non-contamination of the cooling roll was evaluated according to the following <evaluation criteria>.

[0099] <Evaluation Criteria> ◎: No changes were observed on the surface of the cooling roll. ○: Slight dirt is observed on the surface of the cooling roll. △: Dirt is observed on the surface of the cooling roll. ×: The surface of the cooling roll is extremely dirty, resulting in a poor appearance of the molded product.

[0100] (2) Surface resistivity (unit: Ω / sq) The extruded sheets formed in (1) above were measured using a super-insulation meter "DSM-8103" [manufactured by Toa DKK Co., Ltd.] in an atmosphere of 23°C and 40% RH humidity.

[0101] (3) Antistatic properties at low temperatures The extruded sheet molded in (1) above was measured using a super-insulation meter "DSM-8103" [manufactured by Toa DKK Co., Ltd.] under an atmosphere of 10°C and 40% RH to determine its surface resistivity (unit: Ω / sq). The obtained resistance value was defined as (R10). The resistance value obtained in (2) above was designated as (R23), and the value of (R10) / (R23) was evaluated according to the following <evaluation criteria>.

[0102] <Evaluation Criteria> ◎: Less than 1.5 O: 1.5 or higher, less than 2.0 △: 2.0 or higher, less than 2.5 ×: 2.5 or higher

[0103] [Table 2]

[0104] The results in Tables 1 and 2 show that the antistatic agent (Z) of the present invention imparts superior antistatic properties to thermoplastic resins compared to the comparative agent, and is particularly excellent in antistatic properties at low temperatures. Furthermore, it is evident that it exhibits excellent non-contamination of the cooling roll during molding. [Industrial applicability]

[0105] The antistatic agent (Z) of the present invention imparts excellent antistatic properties to thermoplastic resins (E), and is particularly excellent at low temperatures. It imparts excellent antistatic properties to thermoplastic resins. Furthermore, it exhibits excellent continuous moldability (mold contamination) during molding. Therefore, it can be widely used as a material for housing products [for home appliances, office equipment, game consoles, and office equipment, etc.] molded by various molding methods [injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (e.g., casting method, tenter method, and inflation method)], plastic container materials [trays used in clean rooms (IC trays, etc.), other containers, etc.], various cushioning materials, covering materials (packaging films, protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automobile parts, etc.), making it extremely useful.

Claims

1. An antistatic agent (Z) comprising a block polymer (A) having blocks of hydrophobic polymer (a) and blocks of hydrophilic polymer (b) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and at least one salt (S2) selected from the group consisting of alkali metal halides and alkaline earth metal halides.

2. The antistatic agent (Z) according to claim 1, wherein the hydrophobic polymer (a) is at least one selected from the group consisting of polyamide (a1) and polyolefin (a2).

3. The antistatic agent (Z) according to claim 1, wherein the hydrophilic polymer (b) is a polyether (b1).

4. The antistatic agent (Z) according to claim 1, wherein the cation constituting the salt (S1) is imidazolium or sodium.

5. The antistatic agent (Z) according to claim 1, wherein the salt (S2) is an alkali metal halide.

6. The antistatic agent (Z) according to claim 1, wherein the weight ratio of the block polymer (A) to the total weight of the salt (S1) and the salt (S2) [(A) / {(S1)+(S2)}] is 75 / 25 to 98 / 2.

7. The antistatic agent (Z) according to claim 1, wherein the weight ratio of the salt (S1) to the salt (S2) [(S1) / (S2)] is 6 / 94 to 70 / 30.

8. An antistatic resin composition (Y) comprising an antistatic agent (Z) according to any one of claims 1 to 7 and a thermoplastic resin (E).

9. The antistatic resin composition according to claim 8, wherein the weight ratio [(Z) / (E)] of the antistatic agent (Z) to the thermoplastic resin (E) is 3 / 97 to 20 / 80.

10. A molded article obtained by molding the antistatic resin composition (Y) described in claim 8.

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