Antistatic agent for polyolefin resins

Abstract

The object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to thermoplastic resins. [Solution] A block polymer (A) having blocks of polyolefin (a2) and blocks of polyether (b1) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and an alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) are contained in the antistatic agent (Z) for polyolefin resins and a polyolefin resin (E).

Description

[Technical Field]

[0001] This invention relates to an antistatic agent for polyolefin resins. [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 project] [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.

[0005] The present inventors, after diligent research to achieve the above objective, arrived at the present invention. Specifically, the present invention is an antistatic agent (Z) for polyolefin resins, comprising a block polymer (A) having blocks of polyolefin (a2) and blocks of polyether (b1) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and an alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2). [Effects of the Invention]

[0006] The antistatic agent (Z) for polyolefin resin of the present invention has the following effects. (1) It imparts excellent antistatic properties to the molded product. (2) The molded product has excellent appearance.

Mode for Carrying Out the Invention

[0007] <Polyolefin (a2)> The polyolefin (a2) in the present invention is preferably a polyolefin having a reactive group. For example, polyolefin (a21) having reactive groups at both ends and polyolefin (a22) having a reactive group at one end can be mentioned. The reactive group refers to a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, and an isocyanate group.

[0008] <Polyolefin (a21) having reactive groups at both ends> Examples of polyolefin (a21) include polyolefin (a21-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer, polyolefin (a21-2) having a hydroxyl group at both ends of the polymer, polyolefin (a21-3) having an amino group at both ends of the polymer, and polyolefin (a21-4) having an isocyanate group at both ends of the polymer. Among these, from the viewpoints of ease of modification and heat resistance during molding, polyolefin (a21-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer is preferable. In the present specification, "end" means the terminal part where the repeating structure of the monomer units constituting the polymer is interrupted. Also, "both ends" means both ends in the main chain of the polymer.

[0009] Polyolefin (a21) can be obtained, for example, by introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group to both ends of polyolefin (a21-0) mainly composed of a polyolefin whose both ends can be modified. In this context, "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 the polyolefin, 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 the polyolefin, and the weight of polyolefins with modifiable ends is equal to or greater than the weight of polyolefins with modifiable ends, then it shall be considered a polyolefin (a21-0) with polyolefins with modifiable ends as the main component.

[0010] Polyolefins (a21-0) include 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 deconstituted polyolefins {those obtained by mechanically, thermally, or chemically deconstituting high molecular weight [preferably Mn 10,000 to 150,000] polyolefins}. Note that "(co)polymerization" means polymerization or copolymerization.

[0011] Of these, preferred is decontaminated polyolefin, and even more preferred is thermally decontaminated polyolefin, 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. By thermal decontamination, 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.

[0012] Examples of thermally deconjugated polyolefins include those obtained by heating high molecular weight polyolefins in an inert gas (for example, those obtained by heating at 300 to 450°C for 0.5 to 10 hours using the method described in Japanese Patent Publication No. 3-62804) and those that have been thermally deconjugated by heating in air.

[0013] 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.

[0014] 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. 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, butadiene, isoprene, and mixtures thereof having 2 to 12 carbon atoms; more preferred are α-olefins, butadiene, and mixtures thereof having 2 to 10 carbon atoms; and particularly preferred are ethylene and propylene, which are α-olefins having 2 to 3 carbon atoms, and mixtures thereof.

[0015] <Polyolefin (a22) having a reactive group at one end> Examples of polyolefins (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, the preferred material from the viewpoint of ease of modification and heat resistance during molding is polyolefin (a22-1) having a carboxyl group or a carboxylic acid anhydride group at one end of the polymer. Note that "single end" refers to either end of the polymer's main chain.

[0016] Polyolefin (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 polyolefin (a22-0), which mainly consists of a polyolefin with one end that can be modified. In this context, "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 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 as described above is 50% by weight or more of the total weight of polyolefins, and the weight of polyolefins with modifiable ends is greater than the weight of polyolefins with modifiable ends, then it shall be considered a polyolefin (a22-0) with polyolefins with modifiable ends as the main component.

[0017] Polyolefin (a22-0) can be obtained in the same manner as polyolefin (a21-0).

[0018] Polyolefins (a21-0) and polyolefins (a22-0) are generally obtained as mixtures 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 and other factors.

[0019] The following describes the polyolefins (a21-1) to (a21-4) having reactive groups such as carboxyl groups, carboxylic acid anhydride groups, hydroxyl groups, amino groups, and isocyanate groups at both ends of the polymer. However, the polyolefins (a22-1) to (a22-4) having these groups at one end of the polymer can be obtained in the same manner as the polyolefins (a21-1) to (a21-4) by replacing polyolefin (a21-0) with polyolefin (a22-0). The same applies to the preferred polyolefins (a21) and polyolefin (a22).

[0020] As polyolefin (a21-1), polyolefin (a21-1-1) having a structure in which the terminal end of polyolefin (a21-0) is modified with an α,β-unsaturated carboxylic acid (anhydride), polyolefin (a21-1-2) having a structure in which the polyolefin (a21-1-1) is secondarily modified with a lactam or aminocarboxylic acid, polyolefin (a21-1-3) having a structure in which the polyolefin (a21-0) is modified by oxidation or hydroformylation, polyolefin (a21-1-4) having a structure in which the polyolefin (a21-1-3) is secondarily modified with a lactam or aminocarboxylic acid, 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.

[0021] Polyolefin (a21-1-1) can be obtained by modifying polyolefin (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, or their anhydrides, specifically (meth)acrylic acid, maleic acid (or its anhydride), fumaric acid, itaconic acid (or its anhydride), and citraconic acid (or its anhydride). Of these, from the viewpoint of ease of modification, mono- or dicarboxylic acid anhydrides and dicarboxylic acids are preferred, more preferably maleic acid (or its anhydride) and fumaric acid, and particularly preferred maleic acid (or its anhydride). Note that "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0022] Polyolefin (a21-1-2) can be obtained by secondarily modifying polyolefin (a21-1-1) with the above-mentioned lactam or aminocarboxylic acid.

[0023] Polyolefin (a21-1-3) can be obtained by introducing carboxyl groups to polyolefin (a21-0) by oxidation with oxygen and / or ozone (oxidation method) or by hydroformylation by 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. Polyolefin (a21-1-4) can be obtained by secondary modification of polyolefin (a21-1-3) with a lactam or aminocarboxylic acid.

[0024] The acid value of polyolefin (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 polyether (b1). The acid value in this invention can be measured in accordance with JIS K 0070.

[0025] As polyolefin (a21-2), polyolefins having hydroxyl groups obtained by modifying polyolefin (a21-1) with an amine having a hydroxyl group, and mixtures of two or more of these can be used. 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.

[0026] The hydroxyl value of polyolefin (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 polyether (b). The hydroxyl value in this invention can be measured in accordance with JIS K 0070.

[0027] As polyolefin (a21-3), polyolefins having amino groups obtained by modifying polyolefin (a21-1) with a diamine, and mixtures of two or more of these can be used. 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.

[0028] The amine value of polyolefin (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 polyether (b). The amine value in this invention can be measured in accordance with JIS K 1557-7.

[0029] Examples of polyolefins (a21-4) include polyolefins having isocyanate groups obtained by modifying polyolefins (a21-2) with polyisocyanates (those having two or more isocyanate groups), 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.

[0030] As polyolefin (a22-5), polyolefin (a22-5-1) can be used, which has a structure obtained by secondarily modifying a polyolefin (a22-0) with an α,β-unsaturated carboxylic acid anhydride at one end with a diolamine. Examples of diolamines used for secondary modification include diethanolamine.

[0031] The Mn content of polyolefins (a21) and (a22) is preferably 1,000 to 25,000, more preferably 1,500 to 12,000, and particularly preferably 2,000 to 7,000, from the viewpoint of antistatic properties.

[0032] <Polyether (b1)> Examples of polyethers (b1) include polyetherdiols (b1-1), polyetherdiamines (b1-2), and modified products thereof (b1-3). Examples of the polyether diol (b1-1) include those obtained by subjecting a diol (b0) to an addition reaction with an alkylene oxide (hereinafter abbreviated as AO), and specifically, those represented by the general formula (1). H-(OR 1 ) a -O-E 1 -O-(R 2 O) b -H (1) In the general formula (1), E 1 is a residue obtained by removing all hydroxyl groups from the diol (b0). In the general formula (1), R 1 and R 2 are each independently an alkylene group having 2 to 12 carbon atoms, a styrene group, and a chloromethyl group. Among these, an alkylene group having 2 to 4 carbon atoms is preferable. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a 1,2- or 1,3-propylene group, and a 1,2-, 1,3-, 1,4- or 2,3-butylene group. In the general formula (1), a and b are the average number of moles of addition of (OR 1 ) and (R 2 O), and are each independently 1 to 300, preferably 2 to 250, and more preferably 10 to 100. When a and b in the 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.

[0033] Examples of the diol (b0) include aliphatic diols having 2 to 12 carbon atoms, alicyclic diols having 5 to 12 carbon atoms, aromatic diols having 6 to 18 carbon atoms, and tertiary amino group-containing diols etc.

[0034] Examples of aliphatic dihydric alcohols 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 alicyclic dihydric alcohols having 5 to 12 carbon atoms include 1,4-di(hydroxymethyl)cyclohexane and 1,5-di(hydroxymethyl)cycloheptane. 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).

[0035] 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.

[0036] Polyetherdiol (b1-1) can be produced by adding AO to diol (b0). As the aqueous oocyte (AO), 2- to 4-carbon 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 [5- to 12-carbon α-olefin oxides, styrene oxide, and epihalohydrins (epichlorohydrin, etc.)] can also be used in small proportions (30% by weight or less based on the total weight of the AO). 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.

[0037] 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.

[0038] Examples of polyetherdiamines (b1-2) include those represented by general formula (2). H2N-R 3 -(OR 4 ) C -OE 2 -O-(R 5 O)d -R 6 -NH2(2) 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 6 These 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.

[0039] 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.

[0040] 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).

[0041] The Mn content of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 2,000 to 10,000, and most preferably 2,500 to 5,000, from the viewpoint of heat resistance and reactivity with polyolefin (a2).

[0042] <Block polymer (A)> The block polymer (A) in the present invention has a block of polyolefin (a2) and a block of polyether (b1) as constituent units. The polyolefin (a2) and polyether (b1) constituting the block polymer (A) may each be one or two or more types.

[0043] The weight ratio [(a2) / (b1)] of the polyolefin (a2) blocks to the polyether (b1) blocks 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.

[0044] The structures formed by the bonding of a block polymer (A) consisting of a polyolefin (a2) block and a polyether (b1) block include the (a2)-(b1) type, the (a2)-(b1)-(a2) type, the (b1)-(a2)-(b1) type, and the [(a2)-(b1)]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 [(a2)-(b1)]n type, in which polyolefin (a2) and polyether (b1) are repeatedly and alternately bonded. In the [(a2)-(b1)]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, appearance, and mechanical strength (mechanical properties). n is the Mn of the block polymer (A) and 1 This can be determined by 1H-NMR analysis.

[0045] 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 appearance, mechanical strength (mechanical properties), and antistatic properties of the molded product described later.

[0046] If the block polymer (A) has a structure in which a block of polyolefin (a2) and a block of polyether (b1) are linked via ester bonds, amide bonds, ether bonds, or imide bonds, it can be produced, for example, by the following method. Of the above bonds, ester bonds and amide bonds are preferred from an industrial standpoint.

[0047] One method involves placing polyolefin (a2) and polyether (b1) 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, etherification, or imidation reaction (hereinafter abbreviated as "produced water") from the reaction system.

[0048] <Alkyl (alkyl group with 6-18 carbon atoms) benzenesulfonate (S1)> In the present invention, the alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1) (hereinafter also referred to as salt (S1)) is composed of a cation and an anion of alkylbenzenesulfonic acid.

[0049] Examples of alkyl (alkyl with 6 to 18 carbon atoms, preferably 10 to 14 carbon atoms) benzenesulfonic acids include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and octadecylsulfonic acid. Of the alkyl (alkyl group with 6 to 18 carbon atoms) benzenesulfonic acids listed above, dodecylbenzenesulfonic acid is preferred.

[0050] Examples of cations that make up the salt (S1) include alkali metal cations (e.g., lithium, sodium, potassium) and imidazolium cations.

[0051] The imidazolium cations mentioned above include imidazolium cations with 5 to 15 carbon atoms [sometimes abbreviated as C], such as 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1,2,3,4-tetramethylimidazolium cation, and 1-ethyl-2,3-dimethylimidazolium cation. Mu cation, 1,3-dimethyl-2-ethylimidazolium cation, 1,2-dimethyl-3-ethylimidazolium cation, 1,2,3-triethylimidazolium cation, 1,2,3,4-tetraethylimidazolium cation, 1,3-dimethyl-2-phenylimidazolium cation, 1,3-dimethyl-2-benzylimidazolium cation, 1-benzyl-2,3-dimethylimidazolium cation, 4-cyano-1,2,3-trimethylimidazolium 4-Cyanomethyl-1,2-dimethylimidazolium cation, 3-Cyanomethyl-1,2-dimethylimidazolium cation, 4-Acetyl-1,2,3-trimethylimidazolium cation, 3-Acetylmethyl-1,2-dimethylimidazolium cation, 4-Methylcarboxymethyl-1,2,3-trimethylimidazolium cation, 3-Methylcarboxymethyl-1,2-dimethylimidazolium cation, 4-Methoxy-1,2,3 Examples include trimethylimidazolium cation, 3-methoxymethyl-1,2-dimethylimidazolium cation, 4-formyl-1,2,3-trimethylimidazolium cation, 3-formylmethyl-1,2-dimethylimidazolium cation, 3-hydroxyethyl-1,2-dimethylimidazolium cation, 4-hydroxymethyl-1,2,3-trimethylimidazolium cation, and 2-hydroxyethyl-1,3-dimethylimidazolium cation.

[0052] Of the cations constituting the salt (S1), sodium cations and imidazolium cations are preferred from the viewpoint of antistatic properties, sodium cations and 1-alkyl(alkyl with 1 to 3 carbon atoms)3-alkyl(alkyl with 1 to 3 carbon atoms)imidazolium cations are more preferred, and 1-ethyl-3-methylimidazolium cations are particularly preferred.

[0053] <Alkyl (alkyl group with 1-5 carbon atoms) benzenesulfonate (S2)> The alkyl(alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) in this invention is composed of an anion and a cation of alkyl(alkyl with 1 to 5 carbon atoms) benzenesulfonic acid.

[0054] Examples of alkyl (alkyl group with 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms) benzenesulfonic acids include p-toluenesulfonic acid, 4-ethylbenzenesulfonic acid, 4-propylsulfonic acid, 2-sec-butylbenzenesulfonic acid, 4-tert-butylbenzenesulfonic acid, and 4-pentylbenzenesulfonic acid. Of the alkyl (alkyl group with 1 to 5 carbon atoms) benzenesulfonic acids mentioned above, p-toluenesulfonic acid is preferred.

[0055] The cations that make up the salt (S2) are the same as the cations that make up (S1) mentioned above. Of the cations constituting the salt (S2), the preferred ones are sodium cation and imidazolium cation, the more preferred ones are sodium cation and 1-alkyl(alkyl with 1 to 3 carbon atoms)3-alkyl(alkyl with 1 to 3 carbon atoms)imidazolium cation, and the most preferred one is 1-ethyl-3-methylimidazolium cation.

[0056] <Antistatic agent for polyolefin resins (Z)> The antistatic agent (Z) for polyolefin resins of the present invention comprises the block polymer (A), alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2). The antistatic agent (Z) is suitable as an antistatic agent for polyolefin resins for various applications.

[0057] The weight ratio [(A) / {(S1)+(S2)}] of the block polymer (A) to the sum of alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1) and alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) is preferably 90 / 10 to 99 / 1, and more preferably 92 / 8 to 98 / 2. Furthermore, the weight ratio [(S1) / (S2)] of alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1) and alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) is preferably 60 / 40 to 95 / 5, and more preferably 70 / 30 to 90 / 10.

[0058] The antistatic agent (Z) can be manufactured, for example, by the following method (1) or (2). (1) Mix the block polymer (A), salt (S1), and salt (S2). (2) When a polymer of polyolefin (a2) and a polymer of polyether (b1) are reacted by a known method to obtain a block polymer (A), salt (S1) and salt (S2) are added before or during the reaction. The antistatic agent (Z) may contain components other than (A), (S1), and (S2) mentioned above [for example, known resin additives (G) described later], but their weight is preferably 20% by weight or less, and more preferably 0.1 to 5% by weight, based on the weight of (Z).

[0059] <Antistatic resin composition (Y)> The antistatic resin composition (Y) of the present invention contains the above-mentioned antistatic agent (Z) and the polyolefin resin (E) described later. The weight ratio [(Z) / (E)] of the antistatic agent (Z) to the polyolefin resin (E) is preferably 5 / 95 to 25 / 75, and more preferably 10 / 90 to 20 / 80, from the viewpoint of antistatic properties, appearance, and mechanical strength (mechanical properties).

[0060] <Polyolefin resin (E)> Examples of polyolefin resins (E) include polypropylene, polyethylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer. Of the above polyolefin resins (E), polypropylene, polyethylene, and propylene-ethylene copolymer are preferred, and polyethylene is even more preferred.

[0061] The antistatic resin composition (Y) of the present invention may optionally contain known resin additives (G) to the extent that 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 polyolefin 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.

[0062] The antistatic resin composition (Y) of the present invention is obtained by melt-mixing the above-mentioned antistatic agent (Z), polyolefin 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.

[0063] <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.

[0064] The antistatic agent (Z) of the present invention exhibits excellent antistatic properties. Furthermore, it imparts a superior appearance to molded products. 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]

[0065] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. In the following, "parts" refers to parts by weight.

[0066] <Manufacturing Example 1> [Manufacturing of Acid-Modified Polyolefin (a2-1)] In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 100 parts of low molecular weight polypropylene (Mn 4,400, 4.8 double bonds per 1,000 carbon atoms) obtained by thermal reduction [polypropylene produced using a metallocene catalyst [product name "Wintec WSX03", manufactured by Nippon Polypropylene Co., Ltd., MFR 25 (unit is g / 10 min, 230°C, only numerical values ​​are shown below), melting point (measured by differential scanning calorimeter, same applies below) 130°C] was thermally reduced at 370±0.1°C under nitrogen aeration (80 mL / min) for 75 minutes], 10 parts of maleic anhydride, and 27 parts of xylene were charged. After homogeneous mixing, the mixture was melted at 200°C under a nitrogen gas atmosphere (sealed) with stirring and reacted for 10 hours. Subsequently, excess maleic anhydride and xylene were removed by distillation under reduced pressure (less than 1.3 kPa) at 200°C for 3 hours to obtain 95 parts of acid-modified polyolefin (a2-1). The acid value (mgKOH / g) of (a2-1) was 18.5, the manganese content was 4,600, and the melting point was 120°C.

[0067] <Manufacturing Example 2> [Manufacturing of Acid-Modified Polyolefin (a2-2)] In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device, 100 parts of low molecular weight polypropylene (Mn 4,400, 4.6 double bonds per 1,000 carbon atoms) obtained by thermal reduction [polyolefin [product name "Sun Allomer PZA20A", manufactured by Sun Allomer Co., Ltd., Mn 100,000, hereinafter the same] consisting of 98% propylene and 2% ethylene as constituent units, thermal reduction at 370±0.1℃ under nitrogen aeration (80 mL / min) for 75 minutes], 10 parts of maleic anhydride, and 25 parts of xylene were charged. After homogeneous mixing, the mixture was melted at 200℃ under a nitrogen gas atmosphere (sealed) with stirring and reacted for 10 hours. Subsequently, excess maleic anhydride and xylene were removed by distillation under reduced pressure (less than 1.3 kPa) at 200°C for 3 hours to obtain 95 parts of acid-modified polyolefin (a2-2). The acid value (mgKOH / g) of (a2-2) was 17.3, the manganese content was 4,600, and the melting point was 140°C.

[0068] <Manufacturing Example 3> [Manufacturing of Secondarily Modified Acid-Modified Polyolefin (a2-21)] In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and vacuum device, 100 parts of (a2-2) and 5.6 parts of 12-aminododecanoic acid were charged. Under a nitrogen gas atmosphere, the mixture was melted at 200°C with stirring, and the reaction was carried out under reduced pressure (1.3 kPa or less) for 3 hours to obtain 96 parts of secondary modified acid-modified polyolefin (a2-21). The acid value of (a2-21) was 16.6, the Mn content was 4,800, and the melting point was 140°C.

[0069] <Manufacturing Example 4> [Manufacturing of Block Polymer (A-1)] A stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, and depressurization device contains 64.7 parts of acid-modified polyolefin (a2-1), α,ω-diaminoPEG (Mn 2,000, volume resistivity 1 × 10⁻¹⁰). 7 34.7 parts of (b1-1)Ω·cm, 0.1 part of an antioxidant [product name "Irganox 1010", manufactured by BASF Japan Ltd.], and 0.5 parts of zirconyl acetate were charged and polymerized at 220°C under reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer. This polymer was taken out in strand form on a belt and pelletized to obtain a block polymer (A-1) (Mn 25,000, melting point 120°C) consisting of blocks of (a2-1) and blocks of (b1-1).

[0070] <Manufacturing Example 5> [Manufacturing of Block Polymer (A-2)] In Production Example 4, 66.1 parts of secondary modified acid-modified polyolefin (a2-21) and PEG (Mn 3,000, volume resistivity 1 × 10⁻¹⁰) were used instead of (a2-1) 64.7 parts and (b1-1) 34.7 parts. 7 A block polymer (A-2) (Mn 32,000, melting point 140°C) consisting of blocks of (a2-21) and blocks of (b1-2) was obtained in the same manner as in Example 1, except that 33.2 parts of (Ω·cm)(b1-2) were used.

[0071] <Example 1> In a reaction vessel equipped with a stirrer, thermometer, and heating / cooling device, 94.5 parts of block polymer (A-1), 4 parts of 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate (S1-1), and 1.5 parts of 1-ethyl-3-methylimidazolium p-toluenesulfonate (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.

[0072] <Examples 2-5, Comparative Examples 1-3> Each antistatic agent (Z) was obtained in the same manner as in Example 1, except that the compound composition (parts) was as shown in Table 1. The results are shown in Table 1.

[0073] [Table 1]

[0074] <Examples 11-15, Comparative Examples 11-13> According to the formulations shown in Table 2, the antistatic agent (Z) and polyolefin 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.

[0075] <Evaluation Method> (1) Surface resistivity (unit: Ω) In accordance with ASTM D257, the insulation of a test specimen (100 × 100 × 2 mm) was measured using a super-insulation meter "DSM-8103" [manufactured by Toa Denpa Co., Ltd.] in an atmosphere of 23°C and 50% RH humidity.

[0076] (2) Surface resistivity after rinsing (unit: Ω) A test specimen (100 × 100 × 2 mm) was propped up at an angle and washed with 100 ml of deionized water at 23°C and a flow rate of 100 ml / min. It was then dried in a circulating air dryer (80°C) for 3 hours. This washing and drying procedure was repeated a total of 10 times, and the resulting specimens were measured under the same conditions as in (1).

[0077] (3) Appearance of the molded product The molded product described in (1) above was stored in a circulating air dryer at 60°C for 14 days, after which the surface was visually inspected and evaluated according to the following criteria.

[0078] <Evaluation Criteria> ○: Good (No bleed-out material at all) △: Slightly defective (some items have bleed-out) ×: Defective (many items have bleed-out)

[0079] [Table 2]

[0080] Tables 1 and 2 show that the antistatic agent of the present invention provides molded articles with superior antistatic properties and a superior appearance compared to comparable agents. [Industrial applicability]

[0081] The antistatic agent (Z) for polyolefin resins of the present invention can impart excellent antistatic properties, appearance of molded products, and mechanical strength to polyolefin resins. 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) for polyolefin resins comprising a block polymer (A) having blocks of polyolefin (a2) and blocks of polyether (b1) as constituent units, an alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1), and an alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2).

2. The antistatic agent (Z) for polyolefin resin according to claim 1, wherein the cation constituting the alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonate (S1) is imidazolium or sodium.

3. The antistatic agent (Z) for polyolefin resin according to claim 1, wherein the cation constituting the alkyl (alkyl having 1 to 5 carbon atoms) benzenesulfonate (S2) is imidazolium or sodium.

4. The antistatic agent (Z) for polyolefin resin according to claim 1, wherein the weight ratio [(A) / {(S1)+(S2)}] of the block polymer (A) to the sum of the alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1) and the alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) is 90 / 10 to 99 / 1.

5. The antistatic agent (Z) for polyolefin resin according to claim 1, wherein the weight ratio [(S1) / (S2)] of the alkyl (alkyl with 6 to 18 carbon atoms) benzenesulfonate (S1) and the alkyl (alkyl with 1 to 5 carbon atoms) benzenesulfonate (S2) is 60 / 40 to 95 / 5.

6. An antistatic resin composition (Y) comprising an antistatic agent (Z) for polyolefin resins according to any one of claims 1 to 5 and a polyolefin resin (E).

7. The antistatic resin composition according to claim 6, wherein the weight ratio [(Z) / (E)] of the antistatic agent for polyolefin resin (Z) to the polyolefin resin (E) is 5 / 95 to 25 / 75.

8. A molded article obtained by molding the antistatic resin composition (Y) described in claim 6.

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