Antistatic resin composition

Abstract

To provide an antistatic resin composition that imparts excellent antistatic properties and moldability to the resin. [Solution] For thermoplastic resin (A), the following components (B) and (C): Component (B): A block copolymer component having a specific structure that can be obtained by reacting (a) a polyolefin with one end modified with (b) a polyether or a modified version thereof. (C): Fatty acid metal salt It contains, An antistatic resin composition in which the mass ratio of component (B) to component (C) is (B) / (C) = 99.95 / 0.05 to 90 / 10.

Description

Technical Field

[0001] The present invention relates to an antistatic resin composition. More specifically, it relates to an antistatic resin composition that has good moldability in addition to antistatic properties and does not impair the appearance after molding, and further to a film, sheet, and molded body made of the antistatic resin composition.

Background Art

[0002] Generally, synthetic resins are used in various applications such as molded bodies and films due to their excellent properties. However, synthetic resin products are very likely to become electrostatic due to their hydrophobicity. Therefore, they have major drawbacks such as dust and dirt adhering to the products, impairing the appearance, electrical failures occurring during processing, and malfunctioning when used in electronic devices.

[0003] Conventionally, as a means to solve these drawbacks, resin compositions obtained by adding various surfactants such as anionic, cationic, and nonionic surfactants to synthetic resins have been put into practical use. However, the resin composition added with this surfactant is excellent in antistatic properties in the short term after product molding, but it is difficult to maintain the performance over a long period because the surfactant that has bled out on the product surface is lost due to friction, water washing, etc. Furthermore, since the temperature during molding of synthetic resin products is high, the surfactant causes partial thermal decomposition, resulting in smoke generation during molding and coloring of the products. Also, in multilayer films and sheets of synthetic resins, in order to exhibit antistatic performance, it is necessary to add an antistatic agent not only to the surface layer but also to the core layer, so the addition amount increases and there is an economically disadvantageous aspect.

[0004] From this perspective, resin compositions containing polymer-type antistatic agents capable of maintaining long-term antistatic performance have been developed. Polymer-type antistatic agents can solve the problems of surfactants, such as loss of antistatic ability due to friction and washing, and discoloration during thermal decomposition. However, compared to surfactant-type antistatic agents, they are more prone to phase separation due to their high molecular weight. When the matrix resin and the polymer-type antistatic agent are mismatched, phase separation can increase the melt viscosity, leading to a decrease in molding speed, adhesion of antistatic agent components to rolls and molds, and even defects in appearance during molding.

[0005] To address these problems in polymer-type antistatic agents, Patent Document 1 discloses an antistatic film in which a compatibilizer is used to improve compatibility, thereby suppressing defects in the appearance of the film substrate. Patent Document 2 discloses an antistatic resin composition in which moldability is improved by limiting the intrinsic viscosity of the matrix resin. Patent Document 3 discloses an antistatic polypropylene resin laminated foam sheet that exhibits excellent thermoformability and minimal degradation of antistatic performance during thermoforming, by using a polymeric surfactant close to the melting point of the matrix resin. Patent Document 4 discloses an antistatic acrylic resin composition with excellent physical properties and moldability achieved by adding acrylic rubber particles.

[0006] However, Patent Document 1 uses a large amount of polymeric antistatic agent, and its antistatic performance is insufficient. Patent Document 2 has the problem of limiting the matrix resin, and also uses a large amount of polymeric surfactant. Patent Document 3 requires that the melting point of the polymeric antistatic agent be within ±20°C of the melting point of the matrix resin, and further limits the melt flow rate of each compounded resin. Patent Document 4 uses acrylic rubber-based rubber-like particles as an additive, which lowers the tanδ of the acrylic resin composition, limiting its use to applications such as adhesive tapes. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2024-57826 [Patent Document 2] Japanese Patent Publication No. 2008-274031 [Patent Document 3] Patent No. 4540101 [Patent Document 4] Patent No. 4878124 [Overview of the project] [Problems that the invention aims to solve]

[0008] When polymer-type antistatic agents are added to synthetic resin products to impart sufficient antistatic properties, phase separation can occur, leading to an increase in melt viscosity, which can result in a decrease in molding speed, adhesion of antistatic agent components to rolls and molds, and even defects in appearance during molding. Furthermore, even proposals aimed at solving these problems have resulted in insufficient antistatic performance or limited applications for matrix resins and resin compositions. This invention has been made in view of the problems of the prior art and aims to provide an antistatic resin composition that can impart excellent antistatic properties and moldability to resins. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention discovered that the above problems can be solved by blending a specific block copolymer and a fatty acid metal salt in a predetermined ratio with a thermoplastic resin, and thus completed the present invention.

[0010] In other words, the present invention covers the following [1] to

[10] . [1] Thermoplastic resin (A) and The following ingredients (B) and (C): Component (B): At least one block copolymer represented by the following general formula (1) or general formula (2). Component (C): Fatty acid metal salt represented by the following general formula (5) It contains and An antistatic resin composition in which the mass ratio of component (B) to component (C) is (B) / (C) = 99.95 / 0.05 to 90 / 10.

Chem.

Chem.

Chem.

Chem.

[10] [7]. [Effects of the Invention]

[0011] According to the present invention, it is possible to prevent the deterioration of antistatic performance over time due to bleeding, which was observed with surfactant-type antistatic agents, and further improve moldability, thereby providing an antistatic resin composition that yields films, sheets, and molded articles with excellent appearance and antistatic properties. [Modes for carrying out the invention]

[0012] The present invention will be described in more detail below. Component (B) used in the present invention is at least one block copolymer represented by the above general formula (1) or general formula (2). As described later, the block copolymer is a reaction product of (a) a polyolefin with one end modified by acid and (b) a polyether or a modified product thereof.

[0013] In the above general formulas (1) and (2), R 1 , R 3 (and R 4 , R 6 ) is a polyolefin residue, and (a) one end of which is derived from the polyolefin of an acid-modified polyolefin.

[0014] The polyolefins used in (a) the acid-modified polyolefins include polyolefins obtained by polymerizing one or more olefins having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 10 carbon atoms (polymerization method), and low molecular weight polyolefins obtained by the thermal depolymerization method of high molecular weight polyolefins (thermal depolymerization method). The number average molecular weight Mn of the polyolefin is preferably 800 to 20,000, more preferably 1,000 to 10,000, and most preferably 1,500 to 9,000. Examples of olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 2-butene, and isobutene; α-olefins having 5 to 30 carbon atoms, preferably 5 to 12, and more preferably 5 to 10, such as 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, and 1-dodecene; and dienes having 4 to 30 carbon atoms, preferably 4 to 18, and more preferably 4 to 8, such as butadiene, isoprene, cyclopentadiene, and 11-dodecadie Examples include n.

[0015] Furthermore, for the acid modification of polyolefins, for example, α,β-unsaturated carboxylic acids or their anhydrides can be used, specifically monocarboxylic acids, dicarboxylic acids and their anhydrides, such as (meth)acrylic acid, (anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid and (anhydride) citraconic acid. Of these, fumaric acid and (anhydride) maleic acid are preferred.

[0016] (a) Poly(iso)butenyl succinic acid can be preferably used as a polyolefin with one end modified by acid. Poly(iso)butenyl succinic acid can be obtained by reacting poly(iso)butene, which is a homopolymer of isobutene or a copolymer of isobutene and 1-butene, with maleic anhydride. Furthermore, (a) as the polyolefin with one end modified by acid, a polyolefin having an average number of terminal double bonds per molecule of 0.5 to 1.5, preferably 0.7 to 1.0, and preferably polypropylene modified with a dicarboxylic acid such as (anhydride) maleic acid or fumaric acid can be preferably used.

[0017] In the above general formulas (1) and (2), A 1 , A 2 Each of these is a divalent group having a polyoxyalkylene group, and the polyoxyalkylene unit is its constituent (A 1 , A 2 ) preferably contains 20-100% by mass, more preferably 50-100% by mass, and particularly preferably 70-100% by mass. A 1 , A 2 Specifically, this includes polyoxyalkylene groups composed of oxyalkylene groups with 2 to 4 carbon atoms, and -(R 9 O) m -R 8 -(OR 10 ) p -(R 8 R is a divalent organic group with 1 to 30 carbon atoms. 9 , R 10 Examples of groups include alkylene groups with 2 to 4 carbon atoms, where m and p are each independent integers from 1 to 100, and so on.

[0018] (b) Examples of polyethers or modified products thereof include (b1) polyetherdiols, (b2) polyetherdiamines in which the hydroxyl groups of the polyetherdiols are converted to amino groups, (b3) polyethermonools, etc., (b4) modified products of polyethers, and (b5) alkylene oxide adducts of amide alcohols.

[0019] The above (b1) polyetherdiol is obtained by adding alkylene oxide to a diol compound, and in addition to polyethylene glycol and polypropylene glycol, for example, the general formula is: HO-(R 9 O) m -R8 -(OR 10 ) p Examples include compounds represented by -OH. In the formula, R 8 , R 9 , R 10 , m and p are as defined above, but R 8 R is a residue obtained by removing hydroxyl from a diol compound, 9 , R 10 m is an alkylene group having 2 to 4 carbon atoms, and m and p represent the number of alkylene oxide additions per hydroxyl group of the diol. 9 O) and p (OR 10 The oxyalkylene groups may be the same or different, and when they are composed of two or more oxyalkylene groups, the bonding configuration may be block, random, or a combination thereof. m and p are integers from 1 to 100, preferably from 2 to 30, and particularly preferably from 3 to 20. Also, m and p may be the same or different.

[0020] Examples of the above-mentioned diol compounds include dihydric alcohols (for example, aliphatic, alicyclic, or aromatic dihydric alcohols having 2 to 12 carbon atoms), dihydric phenols having 6 to 18 carbon atoms, and tertiary amino group-containing diols. Examples of the above-mentioned aliphatic dihydric alcohols include alkylene glycols (ethylene glycol, propylene glycol), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecanediol, and the like. Examples of alcohols include cyclohexanedimethanol and hydrogenated bisphenol. Examples of aromatic dihydric alcohols include xylylenediol. Examples of the above-mentioned divalent phenols include monocyclic divalent phenols (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, etc.), and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol, etc.).

[0021] Examples of the tertiary amino group-containing diols mentioned above include bishydroxyalkylated compounds of aliphatic or alicyclic primary monoamines having 1 to 30 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) and bishydroxyalkylated compounds of aromatic primary monoamines having 6 to 12 carbon atoms (aniline, benzylamine, etc.). Among these diol compounds, aliphatic dihydric alcohols and bisphenols are preferred, and ethylene glycol and bisphenol A are particularly preferred.

[0022] Examples of alkylene oxides to be added to the above-mentioned diol compound include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide, and one or more of these can be used. The addition of the alkylene oxide is carried out, for example, in the presence of an alkaline catalyst at a temperature of 100 to 200°C.

[0023] In particular, suitable materials for use as (b1) polyetherdiol in the present invention include polyethylene glycol or ethylene oxide adducts of bisphenol A having a molecular weight of 100 to 2,000, more preferably 200 to 1,000.

[0024] Furthermore, the (b2) polyetherdiamine can be obtained by converting the hydroxyl group of the (b1) polyetherdiol to an amino group by a known method, for example, the general formula: H2N-(R 9 O) m -R 8 -(OR 10 ) p Examples include compounds represented by -NH2. In the formula, R 8 , R 9 , R 10 , m and p are the same as those listed in (b1) polyetherdiol above.

[0025] The (b3) polyether monools mentioned above are obtained by adding alkylene oxides to monools such as monohydric alcohols and phenols, for example, the general formula is RO-(AO) k Compounds represented by -H are examples. In the formula, R is a residue obtained by removing a hydroxyl group from any monool, A is an alkylene group having 2 to 4 carbon atoms, and k is the number of alkylene oxide additions. The k (AO) groups may be the same oxyalkylene group or different oxyalkylene groups, and when these are composed of two or more oxyalkylene groups, the bonding configuration may be block, random, or a combination thereof. k is usually an integer from 1 to 200, preferably from 3 to 60, and particularly preferably from 5 to 30.

[0026] Examples of the above monohydric alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, tridecyl alcohol, cetyl alcohol, stearyl alcohol, iso Examples include linear or branched aliphatic saturated alcohols such as stearyl alcohol and synthetic alcohols (e.g., Ziegler alcohol, oxo alcohol), aliphatic unsaturated alcohols such as allyl alcohol, clotyl alcohol, propagyl alcohol, oleyl alcohol, and linoleyl alcohol, aliphatic saturated and unsaturated alcohols such as fragrant alcohol, tallow-reduced alcohol, and coconut oil-reduced alcohol, alicyclic alcohols such as cyclopentanol and cyclohexanol, and aromatic alcohols such as benzyl alcohol and cinnamyl alcohol. In addition to phenol, other phenolic compounds mentioned above include cresol, isopropylphenol, tertiary butylphenol, and tertiary amylphenol. Of these, monohydric alcohols are preferred, and aliphatic monohydric alcohols are even more preferred.

[0027] Examples of modified products of the (b4) polyether include aminocarboxylic acid modified products of (b1) polyetherdiol or (b2) polyetherdiamine, and monocarboxylic acid modified products of (b2) polyetherdiamine. The aminocarboxylic acid modified product can be obtained by reacting (b1) polyetherdiol or (b2) polyetherdiamine with an aminocarboxylic acid or lactam. The monocarboxylic acid modified product can be obtained by reacting (b2) polyetherdiamine with a monocarboxylic acid having 1 to 22 carbon atoms.

[0028] The alkylene oxide adduct of the aforementioned (b5) amide alcohol can be represented, for example, by the following general formula (6), and can be obtained by adding an alkylene oxide to an amide alcohol by a known method. Ra-CONH-Rb-O-(AaO)qH···(6) [In the formula, Ra represents a linear or branched alkyl or alkenyl group having 1 to 21 carbon atoms, Rb represents a linear or branched alkylene group having 1 to 4 carbon atoms, Aa represents an alkylene group having 2 to 4 carbon atoms, and q represents an integer from 1 to 100.]

[0029] The aforementioned amide alcohol can be produced, for example, by amidating an alkanolamine with a carboxylic acid or its reactive derivative (e.g., its ester compound). Examples of alkanolamines include monoethanolamine, n-propanolamine, and isopropanolamine. Examples of carboxylic acids or their reactive derivatives include formic acid, acetic acid, propionic acid, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl behenate, and their alkyl esters.

[0030] Examples of alkylene oxides to be added to the amide alcohol include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide, and one or more of these can be used. The addition of the alkylene oxide can be carried out, for example, in the presence of an alkaline catalyst at a temperature of 80 to 200°C. Furthermore, in the general formula (6) above, q is the number of moles of alkylene oxide added, and is usually an integer from 1 to 100, preferably from 4 to 60, and particularly preferably from 6 to 40. When n is 2 or more and (AaO)q is composed of two or more alkylene oxy groups, the bonding configuration may be block, random, or a combination thereof.

[0031] The block copolymer of component (B) according to the present invention can be obtained by reacting (a) a polyolefin whose one end is acid-modified with (b) a polyether or a modified product thereof. (a) The reaction between an acid-modified polyolefin and (b) a polyether or a modified version thereof can be carried out at 150-250°C, if necessary, in the presence of a catalyst. Specific examples of catalysts include acid catalysts such as sulfuric acid, p-toluenesulfonic acid, and phosphoric acid; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and metal oxides such as calcium oxide, magnesium oxide, zinc oxide, lead oxide, and tin oxide. Furthermore, the catalysts used may include antimony catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide; titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutyl zirconate; organic acid metal salt catalysts such as zirconyl acetate and zinc acetate; palladium catalysts such as palladium acetate and tetrakis(triphenylphosphine)palladium; and combinations of two or more of these. Of these, zirconium catalysts and organic acid metal salt catalysts are preferred, with zirconyl acetate being particularly preferred.

[0032] The ratio of (a) a polyolefin with one end modified by acid and (b) a polyether or a modified thereof is not particularly limited, but in terms of obtaining the block copolymer of the present invention in high yield, a molar ratio of (a) / (b) = 0.8 / 1 to 3 / 1 is preferred.

[0033] The carboxyl group produced by reacting (a) a polyolefin with one end modified by acid with (b) (b1) a polyetherdiol or (b3) a polyethermonool may be neutralized with an alkaline substance. Examples of alkaline substances used for neutralization include hydroxides, carbonates, phosphates, acetates, and sulfates of alkali metals such as lithium, potassium, and sodium, as well as hydroxides and carbonates of alkaline earth metals such as calcium and magnesium, ammonia, and organic amines. Two or more of these may be used in combination. Specifically, examples include, but are not limited to, sodium hydride, potassium hydride, calcium hydride, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium amide, lithium bistrimethylsilylamide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium phosphate, potassium phosphate, calcium phosphate, sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, magnesium sulfate, sodium silicate, lithium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium metaborate, sodium citrate, potassium citrate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, sodium thiosulfate, etc.

[0034] In the present invention, the thermoplastic resin (A) constituting the antistatic resin composition can be a polyolefin resin such as polyethylene or polypropylene, polyvinyl chloride resin, acrylic resin, or the like. Examples of polyethylene-based resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMW-PE), metallocene polyethylene, as well as chlorinated polyethylene (CPE), silane-crosslinked polyethylene, and maleic anhydride-modified polyethylene. Examples of polypropylene-based resins include isotactic polyethylene. Examples include polypropylene (iPP), syndiotactic polypropylene (syn-PP), atactic polypropylene (aPP), ultra-high molecular weight polypropylene (UHMW-PP), metallocene polypropylene, chlorinated polypropylene, silane-crosslinked polypropylene, maleic anhydride-modified polypropylene, and oxidized polypropylene. Other polyolefin resins include olefin homopolymers such as polyisobutylene (PIB), polybutylene (polybutene-1, PB-1), and poly(4-methyl-1-pentene), ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), ethylene-(meth)acrylic acid copolymer (EMAA, EAA), metal salts of ethylene-(meth)acrylic acid copolymer (ionomer resin, ION), ethylene-maleic anhydride copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid ester-maleic anhydride copolymer, and other olefin-based elastomers (TPO) and olefin-based plastomers (POP).

[0035] Furthermore, examples of polyvinyl chloride resins include PVC-S (straight PVC) polymerized with chloroethylene alone, and PVC-M, which is a copolymer with other substances. PVC-S includes soft PVC and hard PVC depending on the amount of plasticizer added, and PVC-M includes vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer, vinyl chloride-vinyl acetate-itaconic acid copolymer, vinyl chloride-vinyl acetate-fumaric acid copolymer, vinyl chloride-vinyl acetate-vinylidene chloride copolymer, vinyl chloride-alkyl vinyl ether copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic acid copolymer, vinyl chloride-vinyl acetate-(meth)acrylic acid ester copolymer, vinyl chloride-vinyl acetate-(meth)acrylic acid ester-(meth)acrylic acid copolymer, etc. Another example of polyvinyl chloride resin is chlorinated polyvinyl chloride (CPVC).

[0036] In addition to highly transparent polymethyl methacrylate resins (PMMA) and other (meth)acrylic acid ester resins, other examples of acrylic resins include methyl methacrylate-butadiene-styrene copolymer (MBS) and methyl methacrylate-styrene copolymer (MS). Other thermoplastic resins include bisphenol A polycarbonate resin (PC), which is produced by the reaction of bisphenol A and phosgene; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT); polyester elastomers (TPEE); acrylonitrile-styrene resin (AS); styrene-butadiene resin (SB); acrylonitrile-butadiene-styrene resin (ABS); acrylonitrile-styrene-acrylic rubber resin (ASA); and acrylonitrile- Examples include ethylene propylene diene styrene resin (AES), silicone acrylonitrile styrene resin (SAS), styrene elastomers (TPS), polyamide resins such as nylon 6 (PA6), nylon 6,6 (PA66), nylon 6,10 (PA610), nylon 4,6 (PA46), nylon 11 (PA11), nylon 12 (PA12), and nylon MXD6 (PAMXD6), polyurethane elastomers (TPU), and polyether block amides in which polyamide blocks and polyether blocks are alternately condensed. Furthermore, the thermoplastic resin (A) may be a blend of two or more of the resins listed above.

[0037] In the antistatic resin composition of the present invention, the mass ratio of thermoplastic resin (A) to component (B) is From the viewpoint of antistatic performance and moldability, the amount of component (B) is preferably 5 to 40 parts, more preferably 7 to 30 parts, and even more preferably 10 to 25 parts per 100 parts of thermoplastic resin (A).

[0038] The component (C) used in the present invention is a fatty acid metal salt represented by the above general formula (5), that is, a metal salt of a fatty acid having 6 to 24 carbon atoms. By blending component (C), a fatty acid metal salt, with the block copolymer of component (B) into the thermoplastic resin (A), the compatibility between component (A) thermoplastic resin and component (B) block copolymer is improved, and phase separation of these components is suppressed, thereby preventing delamination (layered peeling) during injection molding. Furthermore, by using components (B) and (C) in combination, the dispersibility of these components in the thermoplastic resin (A) is improved, resulting in a more uniform composition of the antistatic resin composition. Therefore, the fluidity of the composition becomes uniform, the extrusion amount during molding is stabilized, and it is expected that the homogeneity of products such as films, sheets, and molded articles made from this composition will be improved.

[0039] In the fatty acid metal salt (C) mentioned above, if the number of carbon atoms in the fatty acid is less than 6, the fatty acid itself will volatilize during molding and will not be able to exert its effect. If the number of carbon atoms in the fatty acid exceeds 24, the melting point will be high and the melt viscosity will be high, which may result in poor moldability. Examples of fatty acids with 6 to 24 carbon atoms include saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, arachidic acid, and behenic acid, and unsaturated fatty acids such as 10-hydroxy-2-decenoic acid, un10-hydroxy-2-decenoic acid, do10-hydroxy-2-decenoic acid, tetradecenoic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, and ricinoleic acid. Examples of metals used as the aforementioned metal salts include magnesium, calcium, strontium, and barium as Group 2 metal atoms, zinc as Group 12 metal atoms, and aluminum as Group 13 metal atoms. Among these, metal salts of myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid are preferred from the viewpoint of improving the compatibility between the thermoplastic resin (A) and component (B), with zinc 12-hydroxystearate and magnesium stearate being the most preferred. Unneutralized fatty acids may be included to the extent that they do not impair the effects of the present invention.

[0040] In the antistatic resin composition of the present invention, the mass ratio of component (B) to component (C) (total 100) is (B) / (C) = 99.95 / 0.05 to 90.00 / 10.00, more preferably 99.90 / 0.10 to 95.00 / 5.00, and even more preferably 99.80 / 0.20 to 96.00 / 4.00.

[0041] Furthermore, the resin composition of the present invention may contain other additives such as plasticizers, lubricants, pigments, surfactants, antioxidants, ultraviolet absorbers, antibacterial agents, drying agents, and alcohols, as long as they do not impair the effects of the present invention.

[0042] Examples of the aforementioned plasticizers include phthalates, adipic acids, phosphoric acids, and trimellitic acid epoxy compounds. Examples of the aforementioned phthalates include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), bis(2-ethylhexyl) phthalate (DOP), di-2-ethylhexyl phthalate (DEHP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and bis(2-ethylhexyl) terephthalate (DOTP). Examples of the aforementioned adipic acid derivatives include bis(2-ethylhexyl) adipate (DOA), diisononyl adipate (DINA), di-n-alkyl adipate, diisodecyl adipate (DIDA), diisobutyl adipate, ditridecyl adipate, and dibutoxyethoxyethyl adipate. Examples of the aforementioned phosphate derivatives include tri Examples include methyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. Trimetric acid-based compounds include tris(2-ethylhexyl) trimellitic acid. Epoxy-based compounds include epoxidized soybean oil (ESBO), epoxidized linseed oil (ELSO), epoxidized fatty acid isobutyl, epoxidized fatty acid 2-ethylhexyl, and epoxidized fatty acid octyl esters. These plasticizers can be used individually or in combination of two or more. The amount of plasticizer to be added varies depending on the type of plasticizer, but generally, 1 to 60 parts by mass per 100 parts by mass of thermoplastic resin (A) is preferred.

[0043] Examples of the aforementioned lubricants include fatty acid esters such as butyl stearate and stearyl stearate, alcohols such as stearyl alcohol, glycerin esters such as monoglyceride stearate, amides such as amide stearate, amide oleate, amide erucate, methylenebisstearate, and ethylenebisstearate, and hydrocarbons such as liquid paraffin, paraffin wax, and fine particles of acrylic crosslinked materials. These lubricants can be used individually or in combination of two or more types. The amount added is preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of thermoplastic resin (A).

[0044] Examples of the aforementioned pigments include inorganic pigments and organic pigments. Examples of the aforementioned inorganic pigments include titanium white (titanium dioxide), calcium carbonate, clay, talc, precipitated barium sulfate and barite powder, white carbon, pearl pigments (bismuth oxychloride, basic lead carbonate, titanium oxide-coated mica, etc.), metal powder pigments (aluminum powder, copper powder, brass powder, gold powder, lead powder, tin powder, zinc powder, nickel powder, stainless steel powder, etc.), zinc oxide, zinc sulfide, cadmium-based pigments, lead yellow, lead-based pigments, phosphate-based pigments, chromate-based pigments, molybdate-based pigments, mica-like iron oxide, zinc powder, cuprous oxide, carbon black, iron oxide (iron black), yellow iron oxide, red iron oxide (synthetic or natural), brown iron oxide, Prussian blue, ultramarine blue, chromium oxide, and composite oxide pigments (composite oxide of titanium, antimony, and nickel; composite oxide of iron and zinc; composite oxide of titanium, barium, and nickel; composite oxide of cobalt, aluminum, and chromium, etc.). The aforementioned organic pigments can be broadly classified into azo pigments and polycyclic pigments based on their chemical structure. Among the azo pigments, soluble azo pigments include Lake Red C, Lysol Red BA, Lysol Red CA, Lysol Red SR, Brilliant Carmine 6B, Permanent Red 2B, Bon Red, Bordeaux 10B, and Pigment Rubin G. Insoluble azo pigments include Para Red, Naphthol Orange, Brilliant Fast Scarlet, Naphthol Red FRR, Naphthol Red M, Fast Yellow G, Benzimidazolone Yellow H3G, Disazo Yellow HR, and Balkan Orange. Condensation-type azo pigments include Condensation Azo Yellow 166 and Condensation Azo Red BR. Among polycyclic pigments, phthalocyanine pigments include metal-free phthalocyanine blue, phthalocyanine blue (α-type), and highly chlorinated phthalocyanine green, while condensed polycyclic pigments include anthencelon orange, indigo blue, perinone orange, quinophthalone yellow, dioxazine violet 37, unsubstituted quinacridone red (γ-type), quinacridone magenta, isoindolinone yellow G, nickel complex orange, isoindoline yellow 139, and diketopyrrolopyrrole red 255. Other pigments include fluorescent pigments, aniline black, and alkaline blue toner. When using a pigment, the amount added is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of thermoplastic resin (A), so as not to reduce the strength of the resin.

[0045] Examples of the aforementioned surfactants include well-known anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Examples of anionic surfactants include alkyl sulfates and their salts such as sodium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, and triethanolamine lauryl sulfate; alkyl ether sulfates and their salts such as sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, sodium polyoxyethylene oleyl ether sulfate, and triethanolamine polyoxyethylene lauryl ether sulfate; alkylaryl ether sulfates and their salts such as sodium polyoxyethylene octylphenyl ether sulfate; alkylamide sulfates and their salts such as sodium polyoxyethylene lauric acid amide ether sulfate, sodium polyoxyethylene lauric acid amide ether sulfate, triethanolamine polyoxyethylene myristic acid amide ether sulfate, sodium polyoxyethylene oleic acid amide ether sulfate, sodium polyoxyethylene coconut oil fatty acid amide ether sulfate, and sodium oleic acid amide ether sulfate; and hydrogenated coconut Acyl ester sulfates and their salts, such as sodium glycerol sulfate of oil fatty acids; alkyl sulfonic acids and their salts, such as sodium lauryl sulfonate, sodium myristyl sulfonate, and sodium coconut oil alkyl sulfonate; alkylbenzene sulfonic acids and their salts, such as sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid triethanolamine; alkylnaphthalene sulfonic acids and their salts; formalin condensed sulfonic acids and their salts, such as formalin polycondensates of naphthalene sulfonates; disodium lauryl sulfosuccinate, di-2-ethyl Sulfosuccinic acids and their salts, such as sodium hexyl sulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, and disodium oleamide sulfosuccinate; α-olefin sulfonic acids and their salts, such as sodium dodecenesulfonate, sodium tetradecenesulfonate, potassium dodecenesulfonate, and potassium detrandecenesulfonate; α-sulfo fatty acid esters and their salts, such as methyl α-sulfolaurate, methyl α-sulfomyristate, and methyl esters of ethylene oxide adducts of α-sulfolaurate;N-acylmethyl-taurines and their salts, such as sodium lauroyl-N-methyltaurate, potassium lauroyl-N-methyltaurate, triethanolamine lauroyl-N-methyltaurate, sodium myristoyl-N-methyltaurate, triethanolamine myristoyl-N-methyltaurate, potassium coconut oil fatty acid acyl-N-methyltaurate, sodium coconut oil fatty acid acyl-N-methyltaurate, and triethanolamine coconut oil fatty acid acyl-N-methyltaurate; coconut oil fatty acid N-acylglutamic acids and their salts such as potassium sylglutamate, sodium coconut oil fatty acid acylglutamate, triethanolamine coconut oil fatty acid acylglutamate, sodium lauroylglutamate, potassium myristoylglutamate, sodium myristoylglutamate, sodium palm oil fatty acid acylglutamate, sodium palm oil fatty acid acylglutamate, etc.; sodium N-lauroylglycine, sodium N-myristoylglycine, sodium N-coconut oil fatty acid acylglycine, N -N-acylglycines and their salts, such as potassium coconut oil fatty acid acyl-glycine; acyl isethionates and their salts, such as sodium lauroyl isethionate, sodium myristoyl isethionate, and sodium coconut oil fatty acid acyl isethionate; alkyl sulfoacetates; alkyl ether phosphates and their salts, such as sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, potassium polyoxyethylene myristyl phosphate, sodium polyoxyethylene oleyl ether phosphate, and sodium dipolyoxyethylene oleyl ether phosphate; alkylaryl ether phosphates and their salts; fatty acid amide ether phosphates and their salts, such as sodium polyoxyethylene lauryl amide ether phosphate; alkyl phosphates and their salts, such as sodium lauryl phosphate, sodium myristyl phosphate, sodium coconut oil fatty acid phosphate, potassium myristyl phosphate, triethanolamine lauryl phosphate, diethanolamine oleyl phosphate; lauroyl phosphate; Examples include acyliminodiacetates and their salts, such as sodium nodiacetate, triethanolamine lauroyliminodiacetate, sodium coconut oil fatty acid acyliminodiacetate, disodium lauroyliminodiacetate, and sodium palm kernel fatty acid iminodiacetate; ether carboxylic acids and their salts, such as sodium polyoxyethylene lauryl ether acetate, potassium polyoxyethylene myristyl ether acetate, triethanolamine polyoxyethylene palmityl ether acetate, sodium polyoxyethylene stearyl ether acetate, and sodium polyglyceryl lauryl ether acetate; acylated peptides, such as coconut oil fatty acid silk peptide; amide ether carboxylic acids and their salts, such as sodium polyoxyethylene lauric acid amide ether carboxylate, sodium polyoxyethylene myristic acid amide ether carboxylate, and triethanolamine polyoxyethylene coconut oil fatty acid amide ether carboxylate; acyl lactates; and alkenyl succinic acid and its salts.

[0046] Examples of cationic surfactants include monoalkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut oil alkyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, and cetyltrimethylammonium methyl sulfate; and dialkyl quaternary ammonium salts such as dioctyldimethylammonium chloride, dilauryldimethylammonium chloride, and distearyldimethylammonium chloride. Examples include ammonium salts; triethylmethylammonium methyl carbonate; acylaminoalkyl quaternary ammonium salts such as lanolin fatty acid aminopropyl ethyldimethylammonium ethyl sulfate and lauroylaminoethyl methyldiethylammonium methyl sulfate; alkylisoquinolinium salts such as laurylisoquinolinium chloride; benzalkonium salts such as lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; acyl basic amino acid alkyl ester salts such as N-cocoyl arginine ethyl ester pyrrolidone carboxylate and N-lauroyl lysine ethyl ester hydrochloride; primary amine salts such as laurylamine hydrochloride; secondary amine salts such as dilaurylamine acetate; and tertiary amine salts.

[0047] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as POE (polyoxyethylene) octyl ether, POE (2-ethyl-hexyl) ether, POE lauryl ether, POE myristyl ether, POE cetyl ether, POE stearyl ether, POE oleyl ether, POE isostearyl ether, POE behenyl ether, and polyoxyethylene cetyl stearyl diether; polyoxyethylene polyoxypropylene glycol types such as POE·POP (polyoxypropylene) butyl ether, POE·POP lauryl ether, POE·POP cetyl ether, and POE·POP glycol; and polyoxyethylene alkyl ethers such as POE octylphenyl ether, POE nonylphenyl ether, POE chlorophenyl ether, and POE naphthyl ether. POE hydrogenated castor oil ether; POE castor oil ether; other ethers such as POE lanolin alcohol ether and POE phytosterol; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate and POE glyceryl oleate; polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monolaurate, POE sorbitan monostearate, POE sorbitan tristearate, and POE sorbitan monoisostearate; polyoxyethylene sorbitol fatty acid esters such as POE sorbitol hexastearate, POE sorbitol tetrastearate, POE sorbitol tetraoleate, and POE sorbitol monolaurate; polyethylene glycol monolauric acid, polyethylene glycol monostearate, polyethylene Polyethylene glycol fatty acid esters such as glycol monooleic acid, polyethylene glycol distearate, polyethylene glycol dioleic acid, polyethylene glycol diisostearate; ether esters such as polyethylene glycol lanolin fatty acid esters; glycerin fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monohydroxystearate, glyceryl distearate; polyglycerin fatty acid esters such as diglyceryl monostearate, diglyceryl monooleate, diglyceryl dioleate, diglyceryl monoisostearate, tetraglyceryl monostearate, tetraglyceryl tristearate, tetraglyceryl pentastearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl distearate, decaglyceryl diisostearate; monolaurate Sorbitan fatty acid esters such as sorbitan acetate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, and sorbitan monoisostearate; ethylene glycol fatty acid esters such as ethylene glycol monolaurate and ethylene glycol distearate; propylene glycol fatty acid esters such as propylene glycol monostearate and self-emulsifying propylene glycol monostearate; pentaerythritol fatty acid esters such as pentaerythritol monostearate and pentaerythritol monooleate; sugar derivatives such as maltitol hydroxy fatty acid ether, alkylated polysaccharides, alkyl(poly)glucosides, and sugar esters; alkyl glyceryl ethers such as α-monoisostearyl glyceryl ether; organic acid monoglycerides such as acetyl monoglyceride, lactate monoglyceride, and citrate monoglyceride;Examples include fatty acid alkanolamides such as coconut oil fatty acid monoethanolamide, lauroyl monoethanolamide, myristoyl monoethanolamide, lauroyl diethanolamide, coconut oil fatty acid diethanolamide, lauroyl isopropanolamide, myristoyl isopropanolamide, coconut oil fatty acid isopropanolamide, POE lauroyl monoethanolamide, coconut oil fatty acid methyl monoethanolamide, and coconut oil fatty acid methyl diethanolamide; POE alkylamines such as POE laurylamine and POE stearylamine; and amine oxides such as lauryldimethylamine oxide, cocodimethylamine oxide, and cocoamidopropyldimethylamine oxide.

[0048] Examples of amphoteric surfactants include carboxybetaine-type surfactants such as lauryldimethylbetaine, myristyldimethylbetaine, palmityldimethylbetaine, stearyldimethylbetaine, oleyldimethylbetaine, coconut oil alkyldimethylbetaine, laurylmethylethylbetaine, octadecyloxymethyldimethylbetaine, lauryldihydroxyethylbetaine, stearyldihydroxyethylbetaine, coconut oil alkyldihydroxyethylbetaine, lauramidopropyldimethylbetaine, myristicamidepropyldimethylbetaine, stearateamidepropyldimethylbetaine, oleamidepropyldimethylbetaine, and coconut oil fatty acid amidopropyldimethylbetaine;RN + H2CH2COO - Glycine-type compounds such as laurylglycine, stearylglycine, sodium lauryldiaminoethylglycine, alkylaminoethylglycine chloride, and coconut oil fatty acid acyl-N-carboxyethoxyethyl-N-carboxyethylethylenediamine disodium, indicated by (R: alkyl); RN + H2CH2CH2COO -Aminopropionic acid types such as lauryl-β-alanine and stearyl-β-alanine, indicated by (R: alkyl); sulfobetaine types such as sodium lauryl sulfoacetate, sodium tetradecenesulfonate, sodium di(2-ethylhexyl) sulfosuccinate, lauryldimethylhydroxypropyl sulfobetaine, myristyldimethylhydroxypropyl sulfobetaine, lauryldimethylpropyl sulfobetaine, coconut oil alkyldimethylpropyl sulfobetaine, and lauric acid amidopropyl dimethylhydroxypropyl sulfobetaine; RN + H2CH2CH2SO3 - (R: alkyl) indicates the sulfonic acid type; RN + H2CH2CH2OSO3 - Sulfate forms indicated by (R: alkyl); sodium laurylaminopropionate, sodium laurylaminodipropionate, N-lauroyl-N-hydroxyethyl- N'-Dicarboxyethyl-ethylenediamine disodium, N-Lauroyl-N-hydroxyethyl-N'-carboxyethyl-ethylenediamine sodium, N-Lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium, N-Coconut fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine sodium, N-Lauroyl-N-hydroxyethyl-N'-dicarboxymethyl-ethylenediamine disodium, N-Lauroyl-N-hydroxyethyl-N'-carboxymethyl-ethylenediamine sodium, N-Hydroxydodecyl-N- Aminocarboxylate salt types such as sodium polyoxyethylene-N'-carboxyethyl-N'-polyoxyethyleneethylenediamine and sodium coconut fatty acid acyl-N-hydroxyethylethylenediamine; imidazoline types such as 2-lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-myristyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-stearyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and 2-coconut oil alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; RN +H2CH(CH3)P(OH)O2 - Examples include phosphate-type compounds represented by (R: alkyl); lecithin; and aminoacetic acid betaine types such as lauryldimethylaminoacetic acid betaine and coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine.

[0049] In the antistatic resin composition of the present invention, when a surfactant is used, the amount added is preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of thermoplastic resin (A), from the viewpoint of the surfactant appropriately bleeding to the resin composition interface.

[0050] Examples of the aforementioned antioxidants include phenolic, phosphite, and thioether-based antioxidants. Examples of the aforementioned phenolic antioxidants include 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanuric acid, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, butylidenebis(methyl-butylphenol), 3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionic acid-n-octadecyl, and pentaerythritol=tetrakis[3-(3',5'-di-ter Examples include t-butyl-4'-hydroxyphenyl)propionate, 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl=bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate], and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene. The aforementioned phosphite systems include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[ Examples of thioethers include [d,g] [1,3,2]dioxaphosphosine, tris(2,4-di-tert-butylphenyl) phosphite, trisnonylphenyl phosphite, tetraalkyl(C=12~15)=[propane-2,2-diylbis(4,1-phenylene)]=bis(phosphite), 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, and triphenyl phosphite. Examples of the thioethers include 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate] and ditridecane-1-yl=3,3'-sulfanediyldipropanoate. These antioxidants can be used individually or in combination of two or more, and the preferred amount is 0.03 to 5 parts by mass per 100 parts by mass of thermoplastic resin (A). More preferably, it is 0.05 to 3 parts by mass.

[0051] Examples of the aforementioned UV absorbers include 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 2-[2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 6,6'-bis(2H-benzotriazol-2-yl)-4,4'-bis(2,4,4-trimethylpentan-2-yl)-2,2'-methylenediphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 6,6',6''-(1,3,5-triazine-2,4,6-triyl)tris[3-(hexyloxy)-2-methylphenol], and 2-hydroxy-4-n-octyloxybenzophenone. When using these ultraviolet absorbers, the amount to add is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of thermoplastic resin (A).

[0052] Examples of the aforementioned antibacterial agents include organic antibacterial agents such as chlorine-based, iodine-based, phenol-based, imidazole-based, thiazole-based, or quaternary ammonium compounds; metals such as silver and copper supported on inorganic compounds such as zeolite or zirconium phosphate; and metal oxides such as zinc oxide and titanium oxide. These can be used individually or in combination, and the amount added is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of thermoplastic resin (A).

[0053] Examples of the drying agent include zeolite-based, alumina-based, silica gel-based, clay-based such as desiccant clay, sulfate compounds such as magnesium sulfate, calcium oxide, and calcium chloride. These can be used individually or in combination, and the amount added is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of thermoplastic resin (A).

[0054] Examples of the aforementioned alcohols include monohydric alcohols, dihydric alcohols, and polyhydric alcohols of three or more hydric values. Examples of monohydric alcohols include linear or branched aliphatic saturated alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, tridecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, and synthetic alcohols (e.g., Ziegler alcohol, oxo alcohol); aliphatic unsaturated alcohols such as allyl alcohol, clotyl alcohol, propagyl alcohol, oleyl alcohol, and linoleyl alcohol; aliphatic saturated and unsaturated alcohols such as fragrant alcohol, tallow-reduced alcohol, and coconut oil-reduced alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol; and aromatic alcohols such as benzyl alcohol and cinnamyl alcohol. Examples of dihydric alcohols include hexamethylene glycol, tetramethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4-dihydroxyphenylpropane, and 4,4-dihydroxyphenylmethane. Examples of trihydric or polyhydric alcohols include glycerin, diglycerin, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, sorbitol, and pentaerythritol. The amount of these alcohols added is preferably 0.005 to 1 part by mass, and more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of thermoplastic resin (A).

[0055] In the present invention, when heating and mixing components (B) and (C) with a thermoplastic resin (A) The desired antistatic resin composition can be obtained by any method, such as pre-mixing components (B) and (C) and then adding the mixture to the thermoplastic resin (A) and heating and mixing, or by separately adding components (B) and (C) to the thermoplastic resin (A) and heating and mixing. For example, the thermoplastic resin (A) and component (B) may be mixed using a twin-screw extruder, and then component (C) may be added and mixed further. If other additives are used, they can be added at any stage, for example to the thermoplastic resin (A), component (B), component (C), or a mixture thereof. While single-screw, twin-screw, and multi-screw extruders can be used for heating and mixing, using a twin-screw extruder is preferable in terms of cost and dispersibility. Furthermore, depending on the molding method described later, the components may be heated and mixed in an extruder or the like to form an antistatic resin composition, and then subjected to continuous molding without being removed from the extruder or the like.

[0056] Furthermore, the antistatic resin composition of the present invention can also be obtained via a masterbatch. For example, components (B) and (C) of the present invention can be added to a thermoplastic resin (A), heated and mixed to form a masterbatch. In particular, using a masterbatch allows for uniform dispersion of each component when processed into a molded product.

[0057] Regarding the method for producing the antistatic resin composition of the present invention, when heating and mixing in an extruder or the like, it is desirable to mix the thermoplastic resin (A) and component (B) at a temperature 10 to 30°C or more higher than the melting point or softening point of the thermoplastic resin (A). For example, when the thermoplastic resin (A) is a polypropylene resin, it is preferable to mix at 200 to 260°C, more preferably 210 to 250°C, and even more preferably 220 to 240°C, from the viewpoint of productivity and thermal degradation. Furthermore, even with polyethylene resins, it is preferable to mix at 160 to 250°C, more preferably 170 to 240°C, and even more preferably 180 to 230°C, from the viewpoint of productivity and thermal degradation.

[0058] [Films and sheets made from antistatic resin compositions] The antistatic resin composition of the present invention is a suitable material that can be applied to known and used molding methods, and there are no particular limitations on the molded articles that can be obtained. Examples include films and sheets, monofilaments, multifilaments such as fibers and nonwoven fabrics, injection molded articles, blow molded articles, laminates, foams, and thermoformed articles such as vacuum molded articles. Furthermore, the antistatic resin composition of the present invention has good moldability when stretched, oriented, and crystallized, and the effects of the present invention are clearly evident, making it suitable for the production of stretched films and sheets, tape yarns, stretched blow molded articles, and (mono, multi)filaments.

[0059] Methods for molding the antistatic resin composition of the present invention include injection molding, T-die molding, blow molding (injection stretch blow, extrusion stretch blow, direct blow), balloon molding, inflation molding, co-extrusion, calendering, hot pressing, solvent casting, (stretch) extrusion molding, extrusion lamination with paper or aluminum, shape extrusion molding, thermoforming such as vacuum (pressure) molding, melt spinning (monofilament, multifilament, spunbond method, meltblown method, defibrillation method, etc.), foam molding, and compression molding, and the composition can be adapted to any of these methods.

[0060] In particular, in the case of molding methods that involve crystallization while stretching and oriented, such as extrusion molding or melt spinning, the practical strength and appearance of the resulting molded article, such as strength, heat resistance, impact resistance, and transparency, can be improved, and are therefore more preferably used. The molded article obtained from the antistatic resin composition of the present invention includes, for example, molded articles obtained by known and publicly used molding methods, and there are no restrictions whatsoever on its shape, size, thickness, design, etc.

[0061] Molded articles such as bottles, films or sheets, hollow tubes, laminates, vacuum (pressure) molded containers, (mono, multi) filaments, nonwoven fabrics, and foams, obtained by subjecting the antistatic resin composition according to the present invention to the above molding method, can be used for, for example, shopping bags, paper bags, shrink films, garbage bags, compost bags, lunch boxes, prepared food containers, food and confectionery packaging films, food wrap films, cosmetic and fragrance wrap films, diapers, sanitary napkins, pharmaceutical wrap films, medical wrap films, surgical adhesive film for use with stiff shoulders and sprains, agricultural and horticultural films, agricultural chemical wrap films, greenhouse films, fertilizer bags, packaging bands, film for packaging magnetic tape cassette products such as video and audio, film for packaging flexible discs, film for plate making, adhesive tapes, tapes, and yarns. It can be suitably used as a wide range of materials, including seedling pots, waterproof sheets, sandbags, building films, weed control sheets, vegetation nets, various packaging films for food, electronics, medical, pharmaceuticals, cosmetics, etc., electrical insulation films, metal plate laminating films, glass display films, prism lens sheets for liquid crystal display devices, base films for touch panels, backlights, polarizing plates, optical lenses, covers for various instruments, anti-reflective films used on windows of automobiles, trains, etc.; base films for explosion-proof display films, liquid crystal display substrates, organic EL display element substrates, color filter substrates, touch panel substrates, solar cell substrates, etc.; lens sheets used for optical lenses, screens, etc., and materials used in the electrical and automotive manufacturing industries, agriculture, civil engineering, and fisheries. [Examples]

[0062] Next, the present invention will be described in more detail based on the examples. However, the present invention is not limited to these examples.

[0063] [Production Example 1] Synthesis of Amido Alcohols A nitrogen introduction tube, a stirrer, and a glass flask with a thermometer were charged with 3,205 g of methyl palmitate melted at 80°C. While stirring, a mixture of 731 g of monoethanolamine and 64 g of a 28% sodium methylate methanol solution, which had been prepared in advance, was added dropwise over 5 hours, and the mixture was maintained at 80°C under a nitrogen atmosphere for 5 hours. After that, unreacted monoethanolamine and methanol were removed by desolvation to obtain an amido alcohol in the form of 3,560 g of a viscous liquid. The amine value of the obtained viscous liquid (amido alcohol), with the sodium methylate content subtracted, was 0.01 mg KOH / g. In the IR spectrum, there were characteristic absorptions at O-H stretching 3300 cm -1 , N-H stretching 3100 cm -1 , C=O stretching 1650 cm -1 , N-H bending 1565 cm -1 .

[0064] [Production Example 2] Synthesis of Amido Alcohol Ethylene Oxide Adduct (1) An 802 g of the amido alcohol obtained in Production Example 1 was charged into a stainless steel autoclave with a nitrogen introduction tube, a stirrer, and a thermometer (the same hereinafter), and sufficient nitrogen substitution was carried out. After heating to 80°C while stirring, 470 g of ethylene oxide was introduced over 5 hours, and the reaction was completed by aging at the same temperature for 2 hours. Further, an appropriate amount of an adsorbent [trade name: Kyoward (registered trademark) 700SL (manufactured by Kyowa Chemical Industry Co., Ltd.)] was added for adsorption and filtration to obtain an amido alcohol ethylene oxide adduct (1) in the form of a pale yellow liquid. The hydroxyl value of this adduct (1) was 119 mg KOH / g and the water content was 0.02%.

[0065] [Production Example 3] Synthesis of Amido Alcohol Ethylene Oxide Adduct (2) 267 g of amide alcohol obtained in Production Example 1 was charged into a stainless steel autoclave and thoroughly purged with nitrogen. After raising the temperature to 80°C while stirring, 493 g of ethylene oxide was introduced over 5 hours, and the reaction was completed by aging at the same temperature for 2 hours. An appropriate amount of Kyoward 700SL was then added for adsorption, and the mixture was filtered to obtain amide alcohol ethylene oxide adduct (2) in the form of a pale yellow liquid. The hydroxyl value of this adduct (2) was 66 mg KOH / g, and the water content was 0.01%.

[0066] [Production Example 4] Synthesis of Block Copolymer (B-1) 815 g of polybutenyl succinic acid (saponification value 36 mg KOH / g), 12 g of amide alcohol ethylene oxide adduct (1) (hydroxyl value 119 mg KOH / g) obtained in Production Example 2, 197 g of amide alcohol ethylene oxide adduct (2) (hydroxyl value 66 mg KOH / g) obtained in Production Example 3, and 4 g of antioxidant [product name: ADEKA Stab (registered trademark) PEP-8 (manufactured by ADEKA Corporation), chemical name: 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane] were charged into a stainless steel autoclave. After thorough nitrogen purging and heating to 80°C with stirring, 60 g of 48% KOH aqueous solution and 20 g of potassium acetate aqueous solution were added, and after further thorough nitrogen purging, the temperature was raised to 160°C, and then maintained at 160°C under reduced pressure of 0.2 kPa or less for 4 hours. The resulting product was a viscous polymer. This product is designated as block copolymer (B-1).

[0067] [Manufacturing Example 5] Synthesis of Acid-Modified Polypropylene 9,700 g of low molecular weight polypropylene with a manganese content of 3,300 and an average number of terminal double bonds of 0.9, along with 300 g of maleic anhydride, were charged into a stainless steel autoclave. The mixture was melted at 220°C under a nitrogen gas atmosphere and reacted for 10 hours. Subsequently, the excess maleic acid was removed by distillation under reduced pressure at 200°C for 4 hours to obtain maleic anhydride-modified polypropylene (one-terminal acid-modified polypropylene). The manganese content was 3,400, the saponification value was 30 mg KOH / g, and the degree of acid modification per molecule was 0.9.

[0068] [Production Example 6] Synthesis of Block Copolymer (B-2) In a stainless steel autoclave, 4,000 g of maleic anhydride-modified polypropylene prepared in Production Example 5, 750 g of amide alcohol ethylene oxide adduct (1) obtained in Production Example 2, 46 g of amide alcohol ethylene oxide adduct (2) obtained in Production Example 3, 13 g of antioxidant [product name: Irganox® 1010 (manufactured by BASF Japan Ltd.)], 90 g of 48% NaOH aqueous solution, and 100 g of ionized water were charged. After thorough nitrogen purging, the temperature was raised to 220°C and stirred for 1 hour. The temperature was then maintained at 2 kPa or less for 6 hours to obtain the product. The obtained product was easy to handle and was a solid polymer. The obtained product was designated as block copolymer (B-2).

[0069] Example 1 (Injection Molding) As thermoplastic resin (A), 100 parts by mass of polypropylene resin (A-1) [product name: Novatec® MA1B (manufactured by Nippon Polypropylene Co., Ltd.), MFR 21 g / 10 min] and 2 parts by mass of polyether block amide (A-3) [product name: Pebax® 4033 (manufactured by Arkema)] were blended. As component (B), 10 parts by mass of the block copolymer (B-1) obtained in Production Example 4 was blended. As component (C), 0.05 parts by mass of fatty acid metal salt (C-1) [product name: Magnesium stearate (manufactured by NOF Corporation), general name: magnesium stearate] was blended. The mixture was kneaded in a twin-screw extruder at 230°C, pelletized, and then molded into a plate with a thickness of 1 mm, a length of 70 mm, and a width of 70 mm using an injection molding machine at 230°C. The evaluation results are shown in Table 1.

[0070] Example 7 (Extrusion molding) A sheet with a thickness of 200 μm was fabricated using a T-die extruder at a melting temperature of 230°C. The results are shown in Table 1.

[0071] Examples 2-6 Test specimens were prepared in the same manner as in Example 1, except that component (B) was formulated as shown in Table 1, and the type and amount of the polyether block amide in thermoplastic resin (A) and the fatty acid metal salt in component (C) were changed or omitted. Each specimen was then evaluated. The evaluation results are shown in Table 1.

[0072] Examples 8-9 Test specimens were prepared in the same manner as in Example 7, except that component (B) was formulated as shown in Table 1, and the type and amount of the polyether block amide in thermoplastic resin (A) and the fatty acid metal salt in component (C) were changed or omitted. Each specimen was then evaluated. The evaluation results are shown in Table 1.

[0073] Comparative Examples 1, 2, and 5 Except for omitting component (C) and using the types and amounts of thermoplastic resin (A) and component (B) as shown in Table 1, test specimens were prepared in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

[0074] Comparative Examples 3, 4, and 6 Except for omitting component (C) and using the types and amounts of thermoplastic resin (A) and component (B) as shown in Table 1, test specimens were prepared in the same manner as in Example 7 and evaluated. The evaluation results are shown in Table 1.

[0075] <Evaluation Method> (1) Moldability (ease of peeling from mold and cooling roll) When the antistatic resin compositions of the examples and comparative examples were injection-molded or extrusion-molded, the adhesion situation of the antistatic component (B) etc. to the mold (injection molding machine) or the cooling roll (T-die extruder) was visually confirmed. Those with no adhesion of the antistatic component (B) etc. to the mold or the cooling roll were evaluated as ○, and those with adhesion of even a small amount of component (B) etc. were evaluated as ×.

[0076] (2) Appearance For the test pieces obtained from the antistatic resin compositions of the examples and comparative examples, the appearance defects associated with molding were visually compared and confirmed. When no burrs, stringing, scratches, cracking, shape defects, etc. could be confirmed in the appearance of the test pieces, it was evaluated as 〇, and those with any of burrs, stringing, scratches, cracking, shape defects were evaluated as ×.

[0077] (3) Antistatic property (surface resistivity) After leaving each test piece in an environment of a temperature of 23 °C and a relative humidity of 50% for 1 day, the surface resistivity of the prepared test piece was measured using a resistivity meter [product name: High Resista (registered trademark) UP <MCP-HT450 type> (manufactured by Nitto Seiko Analytic Co., Ltd.)]. The smaller the numerical value, the better the antistatic property. The target for the surface resistivity (LogΩ / □) is 11.0 or less.

[0078] (4) Tack resistance The stickiness (tackiness) of the surface of each test piece was evaluated using a tactile measuring machine [product name: Handy Lab Tester TL701 (manufactured by Trinity Lab Co., Ltd.)]. The smaller the numerical value, the better the tack resistance. The target for the tackiness (Load (gf)) is 20 or less. When the measured value is 20 or less, no stickiness (tackiness) on the surface of the molded product is felt.

[0079] (5) Comprehensive evaluation If the moldability and appearance are 〇, and the antistatic property (11.0 (LogΩ / □) or less) and the tack resistance (20 or less) reach the target values, the comprehensive evaluation is 〇, and if the moldability and appearance are 〇 but the antistatic property does not reach the target value, the comprehensive evaluation is ×.

[0080] [Table 1]

[0081] As shown in Table 1, the test specimens of Examples 1 to 9 exhibited good antistatic performance. As can be seen from the results of Example 5 and Comparative Example 1, it was confirmed that the inclusion of component (C) has almost no adverse effect on the antistatic performance. Furthermore, the test pieces of these examples exhibited excellent moldability and appearance. In other words, the results of these examples confirm that it is possible to provide an antistatic resin composition that yields molded articles with an excellent appearance free from molding defects. On the other hand, in Comparative Examples 1 to 6, results that satisfied all aspects of antistatic properties, appearance, moldability, and tack resistance were not obtained. In particular, as shown in the results for Comparative Examples 3 and 4, when a small amount of component (B) was added (Comparative Example 3), the appearance, moldability, and tack resistance were well maintained, but the antistatic performance was lacking. When the amount of component (B) was increased to achieve the target value of antistatic performance (Comparative Example 4), it was confirmed that it adversely affected the appearance, moldability, and tack resistance. Based on the above results, it was confirmed that the antistatic resin composition according to the present invention has excellent antistatic properties and moldability, and does not impair the appearance of the resin even when kneaded into it.

Claims

1. Thermoplastic resin (A), The following components (B) and (C): Component (B): At least one block copolymer represented by the following general formula (1) or general formula (2). Component (C): Fatty acid metal salt represented by the following general formula (5) It contains and An antistatic resin composition in which the mass ratio of component (B) to component (C) is (B) / (C) = 99.95 / 0.05 to 90 / 10. 【Chemistry 1】 (In the formula, R １ represents a polyolefin residue, A １ represents a divalent group having a polyoxyalkylene group, X １ is -O- or -N(R ２ )-(wherein, R ２ ) represents a hydrogen atom or an alkyl group, alkenyl group, or acyl group having 1 to 22 carbon atoms. １ M represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an alkylaryl group, an acyl group, or a structure represented by the following general formula (3) or the following general formula (4). １ (This represents a hydrogen atom, alkali metal atom, alkaline earth metal atom, ammonium group, or organic ammonium group.) 【Chemistry 2】 (wherein, R ３ represents a polyolefin residue, A ２ represents a divalent group having a polyoxyalkylene group, B ２ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an alkylaryl group, an acyl group, or a structure represented by the following general formula (3) or the following general formula (4).) 【Transformation 3】 (In the formula, R ４ represents a polyolefin residue, X ２ is -O- or -N(R ５ )-(wherein, R ５ ) represents a hydrogen atom or an alkyl group, alkenyl group, or acyl group having 1 to 22 carbon atoms. ２ (This represents a hydrogen atom, alkali metal atom, alkaline earth metal atom, ammonium group, or organic ammonium group.) 【Chemistry 4】 (In the formula, R ６ (This represents a polyolefin residue.) 【Transformation 5】 (wherein n is 2 or 3, R ７ represents a linear or branched alkyl group, alkenyl group, or hydroxyalkyl group having 5 to 23 carbon atoms, M ３ (This represents a Group 2 metal atom, a Group 12 metal atom, or a Group 13 metal atom.)

2. R in the general formula (1) １ The antistatic resin composition according to claim 1, wherein is a polyisobutylene residue.

3. R in the general formula (1) １ This is a polyisobutylene residue, B １ The structure is represented by the general formula (3), and R in the general formula (3) ４ The antistatic resin composition according to claim 1, wherein is a polyisobutylene residue.

4. In the above general formula (2), R ３ This is a polyisobutylene residue, B ２ The structure is represented by the general formula (3), and R in the general formula (4) ６ The antistatic resin composition according to claim 1, wherein is a polyisobutylene residue.

5. A in the above general formula (1) １ , and A in general formula (2) ２ However, -(R ９ O) ｍ -R ８ - ( OR １０ ) ｐ - (wherein, R ８ R is a divalent organic group with 1 to 30 carbon atoms. ９ , R １０ The antistatic resin composition according to claim 1, wherein each of the following is an alkylene group having 2 to 4 carbon atoms, and m and p each independently represent an integer from 1 to 100.

6. A in the above general formula (1) １ is a polyoxyalkylene group, X １ ga-N(R ２ )-(wherein, R ２ The antistatic resin composition according to claim 1, wherein represents an acyl group having 1 to 22 carbon atoms.

7. The antistatic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyolefin resin.

8. A film comprising the resin composition described in claim 7.

9. A sheet made of the resin composition described in claim 7.

10. A molded article comprising the resin composition described in claim 7.

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