Method for producing antistatic resin composition, and resin composition

Abstract

To provide a method for producing an antistatic resin composition capable of imparting excellent antistatic property and anti-tacking property to a resin, and a resin composition.SOLUTION: A method for producing an antistatic resin composition includes a step of heating and mixing the following component (A) and component (B) to a thermoplastic resin, wherein a mass ratio (A) / (B) of the component (A) to the component (B) is 50 / 50 or more and 99 / 1 or less. Component (A): a block copolymer which can be obtained by reacting (a) polyolefin whose one end is modified and (b) polyether or its modified product, and has a specific structure. Component (B): ethylene-unsaturated carboxylic acid-copolymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing an antistatic resin composition and an antistatic resin composition obtained by the method. More specifically, the present invention relates to a method for producing an antistatic resin that has antistatic properties and does not impair appearance or tack resistance even when blended with a resin, an antistatic resin composition obtained by the method, and a film, sheet, and molded article made of the resin composition obtained by the method. [Background technology]

[0002] In general, synthetic resins are used in various applications such as moldings and films due to their excellent properties. However, due to their hydrophobicity, synthetic resin products are very susceptible to static electricity, which has major drawbacks such as dirt and dust adhering to the product and spoiling its appearance, electrical interference during processing, and malfunction when used in electronic devices.

[0003] In the past, as a means for solving these problems, there was a method of adding various surfactants such as anionic, cationic, and nonionic surfactants, which has been put to practical use. However, although this method of adding a surfactant provides excellent antistatic properties for a short period after the product is molded, it is difficult to maintain the performance for a long period of time because the surfactant that bleeds out to the product surface is lost due to friction, washing with water, etc. Furthermore, since the temperature during molding of synthetic resin products is high, the surfactant partially undergoes thermal decomposition, which causes smoke during molding and discoloration of the product. In addition, in synthetic resin multilayer films and sheets, in order to exhibit antistatic properties, it is necessary to add an antistatic agent not only to the surface layer but also to the core layer, which is economically disadvantageous because of the large amount of additive.

[0004] From this viewpoint, polymer-type antistatic agents capable of maintaining antistatic performance for a long period of time have been developed. Although polymer-type antistatic agents can solve the above-mentioned problems of surfactants, such as the loss of antistatic performance due to friction and washing with water, and coloring due to thermal decomposition, the amount of the polymer-type antistatic agent added is larger than that of surfactant-type antistatic agents, and therefore there is a problem that tackiness is easily generated due to the presence of the polymer-type surfactant, which has a relatively smaller molecular weight than the matrix resin, in the surface layer.

[0005] To solve these problems, films and sheets have been proposed that contain a filler (Patent Document 1) or a glycerin polymer (Patent Document 2) as a third component, but the antistatic performance is insufficient and requires the addition of a large amount of polymer additives. Also, a resin composition (Patent Document 3) containing a thermoplastic resin with a glass transition point of 0°C or less and a melting point of 110°C or more and a polymer-type antistatic agent, a melt flow rate of 0.1 to 5 g / 10 min, and a density of 0.900 to 0.940 g / cm 3 A resin composition (Patent Document 4) has been proposed that comprises a linear low-density polyethylene (A), a polypropylene resin (B) having a melt flow rate of 5 to 100 g / 10 min, and a polymeric antistatic agent (C). However, there is a problem in that the resin that can be mixed with the polymeric antistatic agent is limited. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6139844 [Patent Document 2] Patent No. 4894631 [Patent Document 3] JP 2009-95995 A [Patent Document 4] Patent No. 4642499 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0007] When the amount of polymeric antistatic agent added is increased in order to impart sufficient antistatic properties to synthetic resin products, tackiness occurs, and since antistatic properties and tack resistance are in a trade-off relationship, it has been difficult to achieve both. The present invention has been made in consideration of the problems of the prior art, and specifically, an object of the present invention is to provide a method for producing an antistatic resin composition that can impart excellent antistatic properties and tack resistance to resins. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by blending a specific block copolymer and an ethylene-unsaturated carboxylic acid copolymer or an ionomer thereof with a thermoplastic resin in a specified ratio, and mixing the mixture under heating, thereby completing the present invention.

[0009] That is, the present invention covers the following [1] to

[11] . [1] The following components (A) and (B) are added to a thermoplastic resin: Component (A): A block copolymer represented by the following general formula (1) or (2): Component (B): Ethylene-unsaturated carboxylic acid copolymer or its ionomer and mixing the above components by heating. A method for producing an antistatic resin composition, wherein the mass ratio of component (A) to component (B) is (A) / (B)=50 / 50 or more and 99 / 1 or less. [ka] (In the formula, R 1 is a polyolefin residue, A 1 is 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, an alkenyl group or an acyl group having 1 to 22 carbon atoms; B 1represents 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), M 1 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. [ka] (In the formula, R 3 is 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). [ka] (In the formula, R 4 is 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. , M 2 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. [ka] (In the formula, R 6 represents a polyolefin residue. [2] R in the general formula (1) 1 wherein R is a polyisobutylene residue. [3] R in the general formula (1) 1 and R in the general formula (3) 4 wherein R is a polyisobutylene residue. [4] R in the general formula (2) 3 and R in the general formula (4) 6wherein R is a polyisobutylene residue. [5] A in the general formula (1) 1 and A in general formula (2) 2 But -(R 8 O) m -R 7 -(OR 9 ) n -(In the formula, R 7 is a divalent organic group having 1 to 30 carbon atoms, R 8 , R 9 each independently represents an alkylene group having 2 to 4 carbon atoms, and m and n each independently represent an integer of 1 to 100. [6] A in the general formula (1) 1 is a polyoxyalkylene group, and X 1 -N(R 2 )-(wherein, R 2 represents an acyl group having 1 to 22 carbon atoms. [7] Per 100 parts by mass of thermoplastic resin Component (A): 5 to 30 parts by mass of a block copolymer represented by the following general formula (5) or (6): Component (B): 0.005 to 30 parts by mass of an ethylene-unsaturated carboxylic acid copolymer or its ionomer A resin composition comprising: [ka] (In the formula, R 1 is a polyolefin residue, A 1 is 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, an alkenyl group or an acyl group having 1 to 22 carbon atoms; B 1 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 (7) or the following general formula (8), M 1represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. [ka] (In the formula, R 3 is 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 (7) or the following general formula (8). [ka] (In the formula, R 4 is 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. , M 2 represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. [ka] (In the formula, R 6 represents a polyolefin residue. [8] The resin composition according to [7], wherein the thermoplastic resin is a polyolefin resin. [9] A film made of the resin composition described in [7].

[10] A sheet made of the resin composition according to [7].

[11] A molded article made of the resin composition according to [7]. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in further detail below. In the general formulas (1) and (2), R 1 , R 3 , R 4 , R6 is a polyolefin residue, and is a portion derived from a polyolefin of (a) a polyolefin having one end modified with an acid. As the polyolefin, polyolefins obtained by polymerizing one or a mixture of two 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 thermal degradation of high molecular weight polyolefins (thermal degradation method) can be used. 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.

[0011] Examples of the 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 having 5 to 12 carbon atoms, and more preferably having 5 to 10 carbon atoms, such as 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, and 1-dodecene; dienes having 4 to 30 carbon atoms, preferably having 4 to 18 carbon atoms, and more preferably having 4 to 8 carbon atoms, such as butadiene, isoprene, cyclopentadiene, and 11-dodecadiene.

[0012] As the (a) polyolefin modified at one end with an 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, preferably polypropylene modified with a dicarboxylic acid such as maleic acid (anhydride) or fumaric acid can be preferably used.

[0013] In the general formulas (1) and (2), A 1 , A 2 are each a divalent group having a polyoxyalkylene group, and preferably contain polyoxyalkylene units in their constitution at 20 to 100 mass %, more preferably 50 to 100 mass %, and particularly preferably 70 to 100 mass %. Specifically, (b) -(R 8 O)m -R 7 -(OR 9 ) n -(R 7 is a divalent organic group having 1 to 30 carbon atoms, R 8 , R 9 each independently represents an alkylene group having 2 to 4 carbon atoms, and m and n each independently represent an integer of 1 to 100). Examples of the (b) polyether include (b1) polyether diols, (b2) polyether diamines in which the hydroxy groups of the polyether diols are converted to amino groups, and (b3) polyether monols.

[0014] The above (b1) polyether diol is obtained by adding an alkylene oxide to a diol compound, and in addition to polyethylene glycol and polypropylene glycol, for example, a polyether diol having the general formula: HO-(R 8 O) m -R 7 -(OR 9 ) n In the formula, R 7 is the residue obtained by removing the hydroxyl group from a diol compound, R 8 , R 9 represents an alkylene group having 2 to 4 carbon atoms, and m and n represent the number of alkylene oxides added per hydroxy group of the diol. 8 O) and n (OR 9 ) may be the same or different oxyalkylene groups, and when they are composed of two or more kinds of oxyalkylene groups, the bonding form may be block or random, or a combination of these. m and n are usually integers of 1 to 100, preferably 2 to 30, and particularly preferably 3 to 10. m and n may be the same or different.

[0015] The diol compound includes 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 aliphatic dihydric alcohols include alkylene glycols (ethylene glycol, propylene glycol), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohols include cyclohexanedimethanol and hydrogenated bisphenols. Examples of the aromatic dihydric alcohols include xylylenediol. Examples of dihydric phenols include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, etc.), and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

[0016] Examples of tertiary amino group-containing diols include bishydroxyalkylated 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 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.

[0017] The alkylene oxide to be added to the diol compound includes 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 alkali catalyst at a temperature of 100 to 200°C.

[0018] In particular, examples of polyether diol (b1) that can be preferably used in the present invention include polyethylene glycols having a molecular weight of 100 to 2,000, more preferably 200 to 1,000, or ethylene oxide adducts of bisphenol A.

[0019] The (b2) polyetherdiamine can be obtained by converting the hydroxyl groups of the polyetherdiol to amino groups by a known method, and can be represented by, for example, the general formula: HN-(R 8 O) m -R 7 -(OR 9 ) n In the formula, R 7 , R 8 , R 9 , m and n are the same as those exemplified for the polyether diol.

[0020] The (b3) polyether monool can be obtained by adding an alkylene oxide to a monool such as a monohydric alcohol or a phenol, and can be represented by, for example, the general formula: RO-(AO) k In the formula, R represents a residue obtained by removing a hydroxyl group from any monool, A represents an alkylene group having 2 to 4 carbon atoms, and k represents the number of alkylene oxides added. The k (AO)s may be the same or different oxyalkylene groups, and when these are composed of two or more types of oxyalkylene groups, the bonding form may be block or random, or a combination of these. k is an integer of usually 1 to 200, preferably 3 to 60, and particularly preferably 5 to 30.

[0021] Examples of monohydric alcohols include linear or side chain 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, synthetic alcohols (e.g., Ziegler alcohol, oxoalcohol), etc.; aliphatic unsaturated alcohols such as allyl alcohol, crotyl alcohol, propargyl alcohol, oleyl alcohol, linoleyl alcohol, etc.; aliphatic saturated and unsaturated alcohols such as powdered alcohol, beef tallow reduced alcohol, coconut oil reduced alcohol, etc.; alicyclic alcohols such as cyclopentanol, cyclohexanol, etc.; aromatic alcohols such as benzyl alcohol, cinnamyl alcohol, etc.; and phenols such as cresol, isopropyl phenol, tertiary butyl phenol, tertiary amyl phenol, etc., in addition to phenol. Among these, preferred are monohydric alcohols, and more preferred are aliphatic monohydric alcohols.

[0022] Examples of the modified polyether (b4) include an aminocarboxylic acid modified product of (b1) or (b2) and a monocarboxylic acid modified product of (b2). The aminocarboxylic acid modified product can be obtained by reacting (b1) or (b2) with an aminocarboxylic acid or a lactam. The monocarboxylic acid modified product can be obtained by reacting (b2) a polyether diamine or the like with a monocarboxylic acid having 1 to 22 carbon atoms.

[0023] [Block copolymer] The component (A) block copolymer used in the present invention can be obtained by reacting the above-mentioned (a) polyolefin having one end modified with an acid with (b) a polyether or a modified product thereof. The reaction between (a) a polyolefin having one end modified with an acid and (b) a polyether or a modified product thereof can be carried out, if necessary, in the presence of a catalyst at 150 to 250° C. Specific examples of the catalyst include acid catalysts such as sulfuric acid, paratoluenesulfonic acid, phosphoric acid, etc., alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, etc., and metal oxides such as calcium oxide, magnesium oxide, zinc oxide, lead oxide, tin oxide, etc. As the catalyst, antimony-based catalysts such as antimony trioxide, tin-based catalysts such as monobutyltin oxide, titanium-based catalysts such as tetrabutyl titanate, zirconium-based catalysts such as tetrabutyl zirconate, organic acid metal salt-based catalysts such as zirconyl acetate and zinc acetate, palladium-based catalysts such as palladium acetate and tetrakis(triphenylphosphine)palladium, and combinations of two or more of these may be used. Among these, zirconium-based catalysts and organic acid metal salt-based catalysts are preferred, and zirconyl acetate is particularly preferred.

[0024] The charging ratio of (a) polyolefin having one end modified with an acid and (b) polyether 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) of 0.8 / 1 to 3 / 1 is preferred.

[0025] The carboxyl group generated by reacting (a) with (b1) or (b3), etc., may be neutralized with an alkaline substance. Examples of the alkaline substance used for neutralization include hydroxides, carbonates, phosphates, acetates, sulfates, etc. of alkali metals such as lithium, potassium, and sodium, hydroxides and carbonates of alkaline earth metals such as calcium and magnesium, ammonia, organic amines, etc., and combinations of two or more of these. Specific examples include sodium hydride, potassium hydride, calcium hydride, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, n-butyl lithium, sec-butyl lithium, 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 paratoluenesulfonate, potassium paratoluenesulfonate, sodium metaborate, sodium citrate, potassium citrate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and sodium thiosulfate, but are not limited thereto.

[0026] The component (B) ethylene-unsaturated carboxylic acid copolymer used in the present invention is a copolymer having a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid, and may be a block copolymer, a random copolymer, or a graft copolymer. Furthermore, it is not limited to a copolymer consisting of only ethylene and an unsaturated carboxylic acid, and may be a multi-component copolymer in which other copolymerization components are optionally polymerized.

[0027] Examples of the unsaturated carboxylic acid include unsaturated carboxylic acids having 4 to 8 carbon atoms, such as acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, crotonic acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride. Methacrylic acid is particularly preferred. The unsaturated carboxylic acid may be one type or two or more types.

[0028] Examples of the optional other copolymerization components include unsaturated carboxylates such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, dimethyl maleate, and diethyl maleate; unsaturated hydrocarbons such as propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, and 1-hexene; vinyl esters such as vinyl acetate and vinyl propionate; oxides such as vinyl sulfate and vinyl nitrate; halides such as vinyl chloride and vinyl fluoride; vinyl group-containing primary and secondary amine compounds; carbon monoxide; and sulfur dioxide. The above optional copolymerization components may generally be copolymerized at a ratio of 15 mol% or less, preferably 10 mol% or less.

[0029] The ionomer of component (B) ethylene-unsaturated carboxylic acid copolymer used in the present invention means a compound in which at least a part of the acidic groups of the ethylene-unsaturated carboxylic acid copolymer is neutralized with a metal ion, and the metal ion is not particularly limited and examples thereof include alkali metal ions such as lithium, potassium, sodium, cesium, and rubidium, alkaline earth metal ions such as magnesium and calcium, and various metal ions such as aluminum. A preferred metal ion is at least one selected from the group consisting of zinc ion, magnesium ion, potassium ion, and sodium ion, and more preferably zinc ion and sodium ion.

[0030] The ethylene-unsaturated carboxylic acid copolymer or its ionomer, component (B), used in the present invention, preferably has a melting point of 50 to 150°C, more preferably 60 to 130°C, and even more preferably 80 to 110°C, from the viewpoints of dispersibility and tack resistance.

[0031] The ethylene-unsaturated carboxylic acid copolymer or its ionomer, component (B), used in the present invention, preferably has a melt flow rate (MFR) at 190°C under a load of 2,160 g of 0.1 to 300 g / 10 min, more preferably 0.5 to 150 g / 10 min, and even more preferably 0.7 to 80 g / 10 min, from the viewpoints of dispersibility and tack resistance.

[0032] In the present invention, examples of the thermoplastic resin that constitutes the resin composition include polyolefin resins such as polyethylene and polypropylene resins, polyvinyl chloride resins, and acrylic resins. Examples of polyethylene-based materials 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, maleic anhydride modified polyethylene, and polyethylene oxide. Examples of polypropylene-based materials include isotactic 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 polypropylene oxide. Other polyolefins include olefin homopolymers such as polyisobutylene (PIB), polybutylene (polybutene-1, PB-1), and poly(4-methyl-1-pentene), ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-octene copolymers, propylene-1-butene copolymers, ethylene-vinyl acetate copolymers (EVA), ethylene-vinyl alcohol copolymers (EVOH), and ethylene-(meth)acrylic acid ester copolymers, as well as other olefin elastomers (TPO), and olefin plastomers (POP).

[0033] Polyvinyl chloride can be divided into PVC-S (straight PVC), which is polymerized only with chloroethylene, and PVC-M, which is a copolymer with other substances. PVC-S can be divided into soft PVC and hard PVC, depending on the amount of plasticizer added. PVC-M can be 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, and others include chlorinated polyvinyl chloride (CPVC).

[0034] Acrylic resins include (meth)acrylic acid ester resins such as highly transparent polymethyl methacrylate resin (PMMA), as well as methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-styrene copolymer (MS), etc. Other resins include bisphenol A polycarbonate resin (PC) made by the reaction of bisphenol A with 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), acrylonitrile-ethylene polystyrene (PSB), acrylonitrile-ethylene polystyrene (ABS), acrylonitrile-styrene-acrylic rubber (ASA), acrylonitrile-ethylene polystyrene (ABS ... Examples of such thermoplastic resins include propylene diene-styrene resin (AES), silicon-acrylonitrile-styrene resin (SAS), styrene-based elastomer (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), and polyurethane-based elastomer (TPU). Polyolefin resins are particularly useful, and two or more of the above thermoplastic resins may be blended for use.

[0035] In the present invention, the step of heat-mixing the components (A) and (B) with the thermoplastic resin can be carried out by any of the following methods to obtain the desired antistatic resin composition: a method of premixing the components (A) and (B) and then adding the mixture to the thermoplastic resin and heat-mixing it, or a method of separately adding the components (A) and (B) to the thermoplastic resin and heat-mixing it. For example, the thermoplastic resin and the component (B) may be mixed using a twin-screw extruder, and then the component (A) may be added. As the heat-mixing method, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder may be used, but it is preferable to use a twin-screw extruder in terms of cost and dispersibility.

[0036] In addition, in the present invention, the antistatic resin composition can be obtained via a masterbatch. For example, the components (A) and (B) of the present invention can be added to a thermoplastic resin, heated and mixed to form a masterbatch. In particular, by forming the components into a masterbatch, each component can be uniformly dispersed when processed into a molded product.

[0037] In the method for producing the antistatic resin composition of the present invention, when the components are heated and mixed in an extruder or the like, it is desirable to mix them at a temperature 10 to 30° C. higher than the melting point or softening point of the thermoplastic resin and component (B). For example, in the case of polypropylene-based resins, it is desirable to mix them at a temperature of preferably 200 to 260° C., more preferably 210 to 250° C., and even more preferably 220 to 240° C., from the viewpoints of productivity and thermal degradation. Furthermore, in the case of polyethylene-based resins, it is desirable to mix them at a temperature of preferably 160 to 250° C., more preferably 170 to 240° C., and even more preferably 180 to 230° C., from the viewpoints of productivity and thermal degradation.

[0038] In the present invention, the mass ratio of component (A) to component (B) mixed with the thermoplastic resin is from the viewpoint of antistatic performance and tack resistance, 50 / 50 or more and 99 / 1 or less, more preferably 60 / 40 or more and 98.5 / 1.5 or less, and more preferably 70 / 30 or more and 98 / 2 or less.

[0039] The resin composition of the present invention contains the above-mentioned component (A) and component (B), and the content thereof is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 10 to 25 parts by mass, relative to 100 parts by mass of the thermoplastic resin. From the viewpoints of antistatic properties and tack resistance, the content of component (A) of the present invention is preferably 5 to 30 parts by mass, more preferably 7 to 27 parts by mass, and even more preferably 10 to 25 parts by mass, relative to 100 parts by mass of the thermoplastic resin. From the viewpoints of tack resistance and water resistance, the content of component (B) is preferably 0.005 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0040] The resin composition of the present invention can exert a sufficient effect by itself, but may contain, if necessary, a known anionic surfactant, cationic surfactant, nonionic surfactant, or amphoteric surfactant other than that of the present invention, either alone or in combination, as long as the object of the present invention is not impaired. In addition, polymeric antistatic agents such as polyether ester amides, antioxidants, lubricants, colorants, ultraviolet absorbers, and various additives and fillers that are usually added to resin products can also be added as additional components.

[0041] Examples of anionic surfactants include alkyl sulfates and salts thereof, 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 salts thereof, such as sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, sodium polyoxyethylene oleyl ether sulfate, and triethanolamine polyoxyethylene lauryl ether sulfate; alkyl aryl ether sulfates and salts thereof, such as sodium polyoxyethylene octylphenyl ether sulfate; alkyl amide sulfates and salts thereof, such as sodium polyoxyethylene lauric acid amide ether sulfate, triethanolamine polyoxyethylene lauric acid amide ether sulfate, sodium 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; Acyl ester sulfates and their salts, such as sodium hydrogenated coconut oil fatty acid glycerin sulfate; alkyl sulfonic acids and their salts, such as sodium lauryl sulfonate, sodium myristyl sulfonate, and sodium coconut oil alkyl sulfonate; alkyl benzene sulfonic acids and their salts, such as sodium dodecyl benzene sulfonate and triethanolamine dodecyl benzene sulfonate; alkyl naphthalene sulfonic acids and their salts; formalin condensation sulfonic acids and their salts, such as formalin polycondensates of naphthalene sulfonates; disodium lauryl sulfosuccinate, di Sulfosuccinic acids and their salts, such as sodium 2-ethylhexyl sulfosuccinate, disodium polyoxyethylene lauryl sulfosuccinate, and disodium oleamide sulfosuccinate; α-olefin sulfonic acids and their salts, such as sodium dodecene sulfonate, sodium tetradecene sulfonate, potassium dodecene sulfonate, and potassium detradecene sulfonate; α-sulfofatty acid esters and their salts, such as α-sulfolauric acid methyl ester, α-sulfomyristate methyl ester, and α-sulfolauric acid (EO)n methyl ester;N-Acylmethyl-taurines and their salts such as potassium coconut oil fatty acid acyl-N-methyl taurate, sodium lauroyl-N-methyl taurate, potassium lauroyl-N-methyl taurate, triethanolamine lauroyl-N-methyl taurate, sodium myristoyl-N-methyl taurate, triethanolamine myristoyl-N-methyl taurine, sodium coconut oil fatty acid acyl-N-methyl taurate, triethanolamine coconut oil fatty acid acyl-N-methyl taurine, triethanolamine coconut oil fatty acid acyl-N-methyl taurine, etc.; potassium coconut oil fatty acid acyl-glutamate, coconut oil fatty acid acyl-glutarate N-Acylglutamic acid and its salts such as sodium lauroylglutamate, coconut oil fatty acid acyl-glutamic acid triethanolamine, sodium lauroylglutamate, potassium myristoylglutamate, sodium myristoylglutamate, and sodium palm oil fatty acid acyl-glutamate; N-acylglycine and its salts such as sodium N-lauroylglycine, N-myristoylglycine triethanolamine, sodium N-coconut oil fatty acid acyl-glycine, and potassium N-coconut oil fatty acid acyl-glycine; sodium lauroylisethionate, acyl isethionates and their salts, such as sodium myristoyl isethionate and sodium coconut 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; alkyl aryl 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, and diethanolamine oleyl phosphate; acyl iminodiacetic acids and their salts, such as sodium lauroyl iminodiacetate, triethanolamine lauroyl iminodiacetate, sodium coconut oil fatty acid acyliminodiacetate, disodium lauroyl iminodiacetate, and sodium palm kernel fatty acid iminodiacetate;Examples of such ether carboxylic acids and salts thereof include 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 salts thereof such as sodium polyoxyethylene lauric acid amide ether carboxylate, sodium polyoxyethylene myristate amide ether carboxylate, and triethanolamine polyoxyethylene coconut oil fatty acid amide ether carboxylate; acyl lactate; and alkenyl succinic acid and salts thereof.

[0042] Examples of cationic surfactants include monoalkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl ammonium chloride, beef tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, coconut oil alkyl trimethyl ammonium bromide, and cetyl trimethyl ammonium methyl sulfate; dialkyl quaternary ammonium salts such as dioctyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride, and distearyl dimethyl ammonium chloride; triethyl methyl ammonium methyl carbonate; acyl aminoalkyl quaternary ammonium salts such as lanolin fatty acid aminopropyl ethyl dimethyl ammonium ethyl sulfate and lauroyl aminoethyl methyl diethyl ammonium methyl sulfate; dipalmityl poly alkylethenoxy quaternary ammonium salts such as ethenoxyethyl ammonium chloride and distearyl polyethenoxymethyl ammonium chloride; alkylisoquinolinium salts such as lauryl isoquinolinium chloride; benzalkonium salts such as lauryl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride; benzethonium salts such as benzyl dimethyl {2-[2-(p-1,1,3,3-tetramethylbutylphenoxy)ethoxy]ethyl} ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; tributylmethylphosphonium methyl carbonate; 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; tertiary amine salts; fatty acid amide guanidinium salts; and alkyl trialkylene glycol ammonium salts such as lauryl triethylene glycol ammonium hydroxide.

[0043] 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 cetylstearyl diether; polyoxyethylene polyoxypropylene glycol types such as POE·POP (polyoxypropylene) butyl ether, POE·POP lauryl ether, POE·POP cetyl ether, and POE·POP glycol; polyoxyethylene aryl 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 ether types such as POE lanolin alcohol ether and POE phytosterol; 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 fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polyethylene glycol diisostearate; ether esters such as polyethylene glycol lanolin fatty acid ester; glycerin fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate, glyceryl monohydroxystearate, and 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, and decaglyceryl diisostearate; sorbitan fatty acid esters such as sorbitan monolaurate, 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. esters; sugar derivatives such as maltitol hydroxy fatty acid ethers, alkylated polysaccharides, alkyl (poly)glucosides, and sugar esters; alkyl glyceryl ethers such as α-monoisostearyl glyceryl ether; organic acid monoglycerides such as acetyl monoglyceride, lactic acid monoglyceride, and citric acid monoglyceride; 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; amine oxides such as lauryl dimethylamine oxide, coco dimethylamine oxide, and coco amidopropyl dimethylamine oxide;

[0044] Examples of amphoteric surfactants include carboxybetaine-type surfactants such as lauryl dimethyl betaine, myristyl dimethyl betaine, palmityl dimethyl betaine, stearyl dimethyl betaine, oleyl dimethyl betaine, coconut oil alkyl dimethyl betaine, lauryl methyl ethyl betaine, octadecyloxymethyl dimethyl betaine, lauryl dihydroxyethyl betaine, stearyl dihydroxyethyl betaine, coconut oil alkyl dihydroxyethyl betaine, lauric acid amidopropyl dimethyl betaine, myristic acid amidopropyl dimethyl betaine, stearic acid amidopropyl dimethyl betaine, oleic acid amidopropyl dimethyl betaine, and coconut oil fatty acid amidopropyl dimethyl betaine; RN + H2CH2COO - Glycine type such as lauryl glycine, stearyl glycine, sodium lauryl diaminoethyl glycine, alkylaminoethyl glycine chloride, coconut oil fatty acid acyl-N-carboxyethoxyethyl-N-carboxyethylethylenediamine disodium, etc., represented by (R: alkyl); RN + H2CH2CH2COO - Aminopropionic acid types such as lauryl-β-alanine and stearyl-β-alanine, represented by (R: alkyl); sulfobetaine types such as sodium lauryl sulfoacetate, sodium tetradecene sulfonate, sodium di(2-ethylhexyl)sulfosuccinate, lauryl dimethyl hydroxypropyl sulfobetaine, myristyl dimethyl hydroxypropyl sulfobetaine, lauryl dimethyl propyl sulfobetaine, coconut oil alkyl dimethyl propyl sulfobetaine, and lauric acid amidopropyl dimethyl hydroxypropyl sulfobetaine; RN + H2CH2CH2SO3 - Sulfonic acid type represented by (R: alkyl); RN + H2CH2CH2OSO3 -Sulfate type represented by (R: alkyl); sodium laurylaminopropionate, sodium laurylaminodipropionate, disodium N-lauroyl-N-hydroxyethyl-N'-dicarboxyethyl-ethylenediamine, sodium N-lauroyl-N-hydroxyethyl-N'-carboxyethyl-ethylenediamine, sodium N-lauroyl-N'-carboxymethyl-N'-hydroxyethyl-ethylenediamine, sodium N-coconut fatty acid acyl-N'-carboxyethyl-N'-hydroxyethyl-ethylenediamine, sodium N-lauroyl-N-hydroxyethyl-N'-dicarboxymethyl-ethylenediamine, disodium N-lauroyl-N-hydroxyethyl-N'- Aminocarboxylates such as sodium carboxymethyl-ethylenediamine, sodium N-hydroxydodecyl-N-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 of such amino acid betaine types include those represented by the formula (R: alkyl): phosphate; lecithin; and amino acid betaine types such as lauryl dimethyl amino acetate betaine and coconut oil fatty acid amidopropyl dimethyl amino acetate betaine.

[0045] [Film and sheet made of resin composition] The resin composition according to the present invention is a suitable material that can be applied to known and publicly used molding methods, and the molded products obtained are not particularly limited, and examples thereof include films and sheets, monofilaments, multifilaments such as fibers and nonwoven fabrics, injection molded products, blow molded products, laminates, foams, and thermoformed products such as vacuum molded products. Furthermore, the resin composition to which the antistatic agent according to the present invention is added has good moldability when subjected to stretch-oriented crystallization, and the effects of the present invention are prominently exhibited, making it suitable for the production of films and sheets obtained by stretching, tape yarns, stretch-blow molded products, and (mono- and multi-)filaments.

[0046] Methods for molding the resin composition according to the present invention include injection molding, T-die molding, blow molding (injection stretch blow, extrusion stretch blow, direct blow), balloon method, inflation molding, co-extrusion, calendar method, hot press method, solvent casting, (stretch) extrusion molding, extrusion lamination with paper or aluminum, profile extrusion molding, thermoforming such as vacuum (compressed air) molding, melt spinning (monofilament, multifilament, spunbond method, melt blown method, fiber-opening method, etc.), foam molding, compression molding, etc., any of which can be used.

[0047] In particular, in the case of molding methods that can employ a process of stretch-oriented crystallization, such as extrusion molding and melt spinning, the molded article obtained can be improved in practical strength such as strength, heat resistance, impact resistance, transparency, and appearance, and is more preferably used. The molded article obtained from the resin composition according to the present invention includes, for example, molded articles obtained by publicly known and publicly used molding methods, and there are no limitations on the shape, size, thickness, design, etc.

[0048] Molded articles such as bottles, films or sheets, hollow tubes, laminates, vacuum (compressed air) molded containers, (mono, multi) filaments, nonwoven fabrics, and foams obtained by molding the resin composition according to the present invention can be used in a wide range of applications, including, for example, shopping bags, paper bags, shrink films, garbage bags, compost bags, lunch boxes, containers for prepared foods, food and confectionery packaging films, food wrap films, cosmetic and fragrance wrap films, diapers, sanitary napkins, pharmaceutical wrap films, pharmaceutical wrap films, surgical patch medicinal wrap films for use in treating stiff shoulders, sprains, etc., agricultural and horticultural films, agricultural chemical wrap films, greenhouse films, fertilizer bags, packaging bands, films for packaging magnetic tape cassette products such as video and audio, flexible disk packaging films, plate-making films, adhesive tapes, tapes, yarns, seedling pots, It can be suitably used as a wide variety of materials such as waterproof sheets, sandbags, construction films, weed prevention sheets, vegetation nets, various packaging films for food, electronics, medical, pharmaceutical, cosmetics, etc., films for electronic components, electrical insulation films, films for metal plate lamination, films for glass displays, prism lens sheets for liquid crystal display device components, base films for touch panels, backlights, etc., polarizing plates, optical lenses, covers for various instruments, anti-reflection films used in window glass for automobiles, trains, etc.; base films for explosion-proof films for displays, optical sheets such as liquid crystal display substrates, organic EL display element substrates, color filter substrates, touch panel substrates, and solar cell substrates; lens sheets for optical lenses, screens, etc., and materials used in the electrical and automotive manufacturing industries, agriculture, civil engineering, and fisheries. EXAMPLES

[0049] The present invention will now be described in more detail with reference to examples, although the present invention is not limited to these examples.

[0050] [Production Example 1] Synthesis of amide alcohol 3,205 g of methyl palmitate melted at 80°C was charged into a glass flask equipped with a nitrogen inlet tube, stirrer, and thermometer. A previously prepared mixture of 731 g of monoethanolamine and 64 g of 28% sodium methylate in methanol was added dropwise over 5 hours while stirring, and the mixture was maintained at 80°C under a nitrogen atmosphere for 5 hours. Unreacted monoethanolamine and methanol were then removed by desolvation to obtain 3,560 g of a viscous liquid. The amine value of the resulting viscous liquid was 0.01 mg KOH / g, excluding the sodium methylate content. In the IR spectrum, the OH stretch was 3,300 cm -1 , NH telescopic 3100cm -1 , C=O telescopic 1650cm -1 , NH angle angle 1565cm -1 There was a characteristic absorption.

[0051] [Production Example 2] Synthesis of amido alcohol ethylene oxide adduct (1) 802 g of the amide alcohol obtained in Production Example 1 was charged into a stainless steel autoclave equipped with a nitrogen inlet tube, a stirrer, and a thermometer (hereinafter the same), and nitrogen replacement was performed thoroughly. After heating to 80°C with stirring, 470 g of ethylene oxide was introduced over 5 hours, and the mixture was aged at the same temperature for 2 hours to complete the reaction. Furthermore, an appropriate amount of Kyoward (registered trademark) 700SL (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, adsorbed, and filtered to obtain a pale yellow liquid. The hydroxyl value was 119 mgKOH / g, and the moisture content was 0.02%.

[0052] [Production Example 3] Synthesis of amido alcohol ethylene oxide adduct (2) 267 g of the amide alcohol obtained in Production Example 1 was charged into a stainless steel autoclave and thoroughly purged with nitrogen. After heating to 80°C with stirring, 493 g of ethylene oxide was introduced over 5 hours and matured at the same temperature for 2 hours to complete the reaction. An appropriate amount of Kyoward 700SL (Kyowa Chemical Industry Co., Ltd.) was added and absorbed, and the mixture was filtered to obtain a pale yellow liquid. The hydroxyl value was 66 mgKOH / g and the moisture content was 0.01%.

[0053] [Production Example 4] Synthesis of block copolymer (A-1) A stainless steel autoclave was charged with 815 g of polybutenyl succinic acid (saponification value: 36 mg KOH / g), 12 g of the amide alcohol ethylene oxide adduct (1) obtained in Production Example 2 (hydroxyl value: 119 mg KOH / g), 197 g of the amide alcohol ethylene oxide adduct (2) obtained in Production Example 3 (hydroxyl value: 66 mg KOH / g), and 4 g of an antioxidant [ADEKA STAB (registered trademark) PEP-8 (product name: manufactured by ADEKA CORPORATION), 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane]. After sufficient nitrogen replacement and heating to 80°C while stirring, 60g of 48% KOH and 20g of potassium acetate solution were added, and sufficient nitrogen replacement was performed again, heating to 160°C, and maintaining at 160°C and a reduced pressure of 0.2kPa or less for 4 hours. The product was a viscous polymer. The product was designated as block copolymer (A-1).

[0054] [Production Example 5] Synthesis of acid-modified polypropylene 9,700g of low molecular weight polypropylene with Mn of 3,300 and average number of terminal double bonds of 0.9 and 300g of maleic anhydride were melted at 220°C under a nitrogen gas atmosphere and reacted for 10 hours. Then, excess maleic acid was distilled off under reduced pressure at 200°C for 4 hours to obtain a maleic anhydride modified polypropylene (single-terminal acid modified). Mn was 3,400, saponification value was 30mgKOH / g, and degree of acid modification per molecule was 0.9.

[0055] [Production Example 6] Synthesis of block copolymer (A-2) In a stainless steel autoclave, 4,000 g of the maleic anhydride modified polypropylene prepared in Production Example 5, 750 g of the amide alcohol ethylene oxide adduct (1) obtained in Production Example 2, 46 g of the amide alcohol ethylene oxide adduct (2) obtained in Production Example 3, 13 g of an antioxidant (Irganox (registered trademark) 1010), 90 g of 48% NaOH, and 100 g of ionized water were charged. After sufficient nitrogen replacement and heating to 220°C, stirring was carried out for 1 hour. The pressure was further maintained at 2 kPa or less for 6 hours to obtain a product. The obtained product was easy to handle and was a solid polymer. The obtained product was designated as block copolymer (A-2).

[0056] Example 1 (Injection Molding) 20 parts by mass of the block polymer (A-1) obtained in Production Example 4 and 1 part by mass of an ethylene-methacrylic acid copolymer (B-1) (MFR 33 g / 10 min) were blended with 100 parts by mass of a polypropylene resin [Novatec (registered trademark) MA1B (trade name: manufactured by Japan Polypropylene Co., Ltd.), MFR 21 g / 10 min] as a thermoplastic resin, and the mixture was kneaded at 230°C in a twin-screw extruder, pelletized, and molded into a plate shape of 1 mm thick, 70 mm long, and 70 mm wide at 230°C in an injection molding machine. The evaluation results are shown in Table 1.

[0057] Example 4 (Extrusion) 20 parts by mass of the block copolymer (A-1) of Production Example 4 and 5 parts by mass of an ethylene-methacrylic acid copolymer (B-1) (MFR 33g / 10min) were blended with 100 parts by mass of a polyethylene resin [Novatec LL UF-240 (trade name: manufactured by Japan Polypropylene Co., Ltd.), MFR 2.1g / 10min] as a thermoplastic resin, and a sheet having a thickness of 200 μm was formed at a melt temperature of 230° C. using a T-die extruder. The evaluation results are shown in Table 1.

[0058] Examples 2 to 3, Examples 6 to 9, Comparative Example 2 Test pieces were prepared and evaluated in the same manner as in Example 1, except that the types and amounts of components (A) and (B) were as shown in Table 1. The evaluation results are shown in Table 1.

[0059] Examples 5 and 10 Test pieces were prepared and evaluated in the same manner as in Example 5, except that the types and amounts of components (A) and (B) were as shown in Table 1. The evaluation results are shown in Table 1.

[0060] Comparative Examples 1 and 5 Test pieces were prepared and evaluated in the same manner as in Example 1, except that the component (B) was a propylene-maleic anhydride copolymer or was not added. The evaluation results are shown in Table 1.

[0061] Comparative Examples 3, 4, and 6 Test pieces were prepared and evaluated in the same manner as in Example 5, except that 1,8-octanedicarboxylic acid or no addition was used as the component (B). The evaluation results are shown in Table 1.

[0062] <Evaluation method> (1) Appearance A test piece containing no additive was visually compared with a test piece obtained by the method for producing an antistatic resin composition of the present invention. Test pieces that had the same appearance as the unadded test piece and were compatible with the resin were rated as ◯, whereas test pieces that had poor appearance due to the occurrence of streaks, voids, fish eyes, etc. were rated as ×.

[0063] (2) Hue A test piece containing no additive was visually compared with a test piece containing the antistatic resin composition of the present invention. Test pieces that were compatible with the resin and had the same hue as the test piece containing no additive were rated as ◯, and test pieces that were yellowed were rated as ×.

[0064] (3) Antistatic properties (surface resistivity) After leaving the specimens for one day in an environment with a temperature of 23°C and a relative humidity of 50%, the surface resistivity of the specimens was measured using a resistivity meter (Hiresta (registered trademark)-UP MCP-HT450 manufactured by Nitto Seiko Analytech Co., Ltd.). The smaller the value, the better the antistatic properties. The target surface resistivity (LogΩ / □) is 11 or less.

[0065] (4) Tack resistance The stickiness (tackiness) of the surface was evaluated using a tactile measuring device (Handy Lab Tester TL701 manufactured by Trinity Lab Co., Ltd.). The smaller the value, the better the tack resistance. The target tackiness (Load (gf)) is 20 or less. If the measured value is 20 or less, the surface of the molded product will not feel sticky (tacky).

[0066] (5) Overall rating If the appearance was rated as ◯ and the antistatic property and tack resistance reached the target values, the overall evaluation was rated as ◯. If the appearance was rated as ×, or if the appearance was rated as ◯ but the antistatic property or tack resistance did not reach the target values, the overall evaluation was ×.

[0067] [Table 1]

[0068] As shown in Table 1, in Examples 1 to 10, even when the ethylene-unsaturated carboxylic acid copolymer or its ionomer was contained, there was almost no change in the antistatic performance. Furthermore, similar to the test pieces containing no additives, the test pieces had an excellent appearance without streaks, voids, fish eyes, etc., and further had excellent tack resistance. On the other hand, in Comparative Examples 1 to 6, satisfactory results were not obtained in all of the antistatic properties, appearance, and tack resistance. From the above results, it was confirmed that the resin composition obtained by the method for producing an antistatic resin composition according to the present invention has excellent antistatic properties and does not impair the appearance or tack resistance even when kneaded into a resin.

Claims

1. The thermoplastic resin is mixed with the following components (A) and (B): Component (A): A block copolymer represented by the following general formula (1) or (2): Component (B): Ethylene-unsaturated carboxylic acid copolymer or its ionomer and mixing the above components by heating. A method for producing an antistatic resin composition, wherein the mass ratio of component (A) to component (B) is (A) / (B)=50 / 50 or more and 99 / 1 or less. 【Chemistry 1】 (In the formula, R １ is a polyolefin residue, A １ is 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, an alkenyl group or an acyl group having 1 to 22 carbon atoms; B １ 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), M １ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. 【Chemistry 2】 (In the formula, R ３ is 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): 【Chemistry 3】 (In the formula, R ４ is 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. , M. ２ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. 【Chemistry 4】 (In the formula, R ６ represents a polyolefin residue.)

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

3. R in the general formula (1) １ and R in the general formula (3) ４ The method for producing an antistatic resin composition according to claim 1, wherein is a polyisobutylene residue.

4. R in the general formula (2) ３ and R in the general formula (4) ６ is a polyisobutylene residue A method for producing the antistatic resin composition according to claim 1.

5. In the general formula (1), A １ and A in general formula (2) ２ But -(R ８ O) ｍ -R ７ - (OR ９ ) ｎ - (wherein, R ７ is a divalent organic group having 1 to 30 carbon atoms; R ８ , R ９ each independently represents an alkylene group having 2 to 4 carbon atoms, and m and n each independently represent an integer of 1 to 100.

6. In the general formula (1), A １ is a polyoxyalkylene group, and X １ -N(R ２ )-(wherein, R ２ represents an acyl group having 1 to 22 carbon atoms.

7. For 100 parts by mass of thermoplastic resin Component (A): 5 to 30 parts by mass of a block copolymer represented by the following general formula (5) or (6): Component (B): A resin composition containing 0.005 to 30 parts by mass of an ethylene-unsaturated carboxylic acid copolymer or an ionomer thereof. 【Chemistry 5】 (In the formula, R １ is a polyolefin residue, A １ is 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, an alkenyl group or an acyl group having 1 to 22 carbon atoms; B １ 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 (7) or the following general formula (8), M １ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. 【Chemistry 6】 (In the formula, R ３ is 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 (7) or the following general formula (8). 【Chemistry 7】 (In the formula, R ４ is 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. , M. ２ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic ammonium group. 【Chemistry 8】 (In the formula, R ６ represents a polyolefin residue.)

8. The resin composition according to claim 7, wherein the thermoplastic resin is a polyolefin resin.

9. A film comprising the resin composition according to claim 7.

10. A sheet comprising the resin composition according to claim 7.

11. A molded article made of the resin composition according to claim 7.

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